Bis(aminophenoxy)-alpha-substituted stilbenes

ABSTRACT

bis(Aminophenoxy)-alpha-substituted stilbenes are prepared by reacting a dihydroxy-alpha-substituted stilbene with a halonitrobenzene in the presence of a basic acting substance such as potassium carbonate and hydrogenating the resulting bis(nitrophenoxy)-alpha-substituted stilbene to convert the nitro groups to amino groups. These compounds are useful as curing agents for epoxy resins.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 08/058,100 filed May 6,1993, now U.S. Pat. No. 5,300,594.

FIELD OF THE INVENTION

The present invention concerns bis(aminophenoxy)-alpha-substitutedstilbenes, curable (thermosettable) mixtures thereof with one or moreepoxy resins, as well as the cured (thermoset) compositions thereof.

BACKGROUND OF THE INVENTION

The present invention provides novel bis(aminophenoxy)-alpha-substitutedstilbenes which are useful for curing epoxy resins. Epoxy resins arewell established as a class of curable compositions which find efficacyin a myriad of applications. The curing of epoxy resins is effected by awide range of curing agents including, for example, the primary andsecondary aliphatic, cycloaliphatic and aromatic polyamines;dicarboxylic acids and the anhydrides thereof; aromatic hydroxylcontaining compounds; imidazoles; guanidines; ureaaldehyde resins andalkoxylated derivatives thereof; melamine-aldehyde resins andalkoxylated derivatives thereof; amidoamines; epoxy resin adducts; andvarious combinations thereof. In many of the applications served byepoxy resins, it would be desirable to improve one or more of thephysical and/or mechanical and/or thermal properties of the curedproducts thereof. The bis(aminophenoxy)-alpha-substituted stilbenes ofthe present invention are also of useful for preparation of otherthermoset polymers, such as, for example, polyurethanes and polyureas.

The bis(aminophenoxy)-alpha-substituted stilbenes of the presentinvention possess a unique molecular structure heretofore unavailable inan epoxy resin curing agent. One of the features of the molecularstructure inherent to the bis(aminophenoxy)-alpha-substituted stilbenesof the present invention is the alpha-substituted stilbene moiety whichis a mesogen, especially when 4,4'-disubstitution predominates. A secondfeature of the molecular structure inherent to thebis(aminophenoxy)-alpha-substituted stilbenes of the present inventionis the presence of an ether linkage between each aromatic ring of thealpha-substituted stilbene moiety and each aromatic ring of theaminoaryl group. These ether linkages provide flexibility, thusdecoupling the aromatic rings possessing the amino groups from themesogenic moiety (alpha-substituted stilbene). A third feature of themolecular structure inherent to the bis(aminophenoxy)-alpha-substitutedstilbenes of the present invention is the presence of the amino groupson the aromatic rings which are decoupled from the mesogenic moiety viathe ether linkages, such that the amino group may be present at anyposition on the decoupled aromatic ring. Variation of the amino groupsubstitution on the aromatic rings leads to a high degree of controlover the type of liquid crystallinity achievable in certain of thecurable compositions prepared therefrom and, surprisingly, liquidcrystallinity can still be achieved even with ortho substitution by theamino group. The combination of molecular structures inherent to thebis(aminophenoxy)-alpha-substituted stilbenes of the present inventionprovides curable epoxy resin compositions with outstandingprocessability and cured epoxy resin compositions thereof withsubstantial improvements in one or more physical and/or mechanicaland/or thermal properties.

SUMMARY OF THE INVENTION

One aspect of the present invention pertains tobis(aminophenoxy)-alpha-substituted stilbenes represented by thefollowing Formula I ##STR1## wherein each R is independently hydrogen ora hydrocarbyl or hydrocarbyloxy group having from one to about 10,preferably one to about 4, carbon atoms, a halogen atom, preferablychlorine, bromine or fluorine, a nitro group, a nitrile group or a--CO--R² group; each R¹ is independently hydrogen or a hydrocarbyl grouphaving from one to about 10, preferably one to about 6, carbon atoms; Xis a ##STR2## group, each R² is independently hydrogen or a hydrocarbylgroup having from one to about 10, preferably one to abut 2, carbonatoms; R³ is a hydrocarbyl group having from one to about 10, preferablyone to about 2, carbon atoms and may be chlorine or a nitrile group,when n has a value of zero; and n has a value of zero or one.

Another aspect of the present invention pertains to curable(thermosettable) compositions comprising (A) a curing amount of one ormore bis(aminophenoxy)-alpha-substituted stilbenes and (B) one or moreepoxy resins.

A further aspect of the present invention pertains to curablecompositions which have been subjected to the application of an electricfield or magnetic field or drawing and/or shear flow before and/orduring curing or processing of the aforesaid curable compositions andwherein said bis(aminophenoxy)-alpha-substituted stilbene is mesogenic.

A further aspect of the present invention pertains to products resultingfrom curing the aforementioned curable compositions.

A still further aspect of the present invention pertains to a processfor preparing bis(aminophenoxy)-alpha-substituted stilbenes whichcomprises (1) reacting a dihydroxy-alpha-substituted stilbene with ahalonitrobenzene in the presence of a basic acting substance; followedby (2) hydrogenating the resultant bis(nitrophenoxy)-alpha-substitutedstilbene to convert the nitro groups to amino groups and thereafterrecovering the thus prepared bis(aminophenoxy)-alpha-substitutedstilbene.

DETAILED DESCRIPTION OF THE INVENTION DEFINITIONS

The term "hydrocarbyl" as employed herein means any aliphatic,cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphaticor aliphatic or cycloaliphatic substituted aromatic groups. Thealiphatic or cycloaliphatic groups can be saturated or unsaturated.Likewise, the term "hydrocarbyloxy" means a hydrocarbyl group having anoxygen linkage between it and the carbon atom to which it is attached.

The term "mesogenic" or "mesogen" as is used herein designates compoundscontaining one or more rigid rodlike structural units which have beenfound to favor the formation of liquid crystal phases in the case of lowmolar mass substances. Thus the mesogen or mesogenic moiety is thatstructure responsible for molecular ordering. The term mesogenic isfurther defined by R. A. Weiss (ed.) and C. K. Ober (ed.) inLiquid-Crystalline Polymers, ACS Symposium Series 435 (1989) on pages1-2: "The rigid unit responsible for the liquid crystalline behavior isreferred to as the mesogen," and "Liquid crystalline order is aconsequence solely of molecular shape anisotropy, such as found in rigidrodshaped molecules . . . " and "Liquid crystal is a term that is nowcommonly used to describe materials that exhibit partially ordered fluidphases that are intermediate between the three dimensionally orderedcrystalline state and the disordered or isotropic fluid state. Phaseswith positional and/or orientational long-range order in one or twodimensions are termed mesophases. As a consequence of the molecularorder, liquid crystal phases are anisotropic, i.e., their properties area function of direction." Further definition of the term mesogenic maybe found in Polymeric Liquid Crystals, Alexandre Blumstein (ed.), (1983)on pages 2-3: "Compounds forming small molecule thermotropic liquidcrystals usually have the following molecular structural features:--highlength:breadth (axial) ratio--rigid units such as 1,4-phenylene,1,4-bicyclooctyl, 1,4-cyclohexyl, etc.,--rigid central linkages betweenrings such as --COO--, --CH═CH--, --N═NO--, --N═N--, etc.--anisotropicmolecular polarization."

The terms "curable" and "thermosettable" are used synonamouslythroughout and mean that the composition is capable of being subjectedto conditions which will render the composition to a cured or thermosetstate or condition.

The terms "cured" and "thermoset" are used synonamously throughout. Theterm "thermoset is defined by L. R. Whittington in Whittington'sDictionary of Plastics (1968) on page 239: "Resin or plastics compoundswhich in their final state as finished articles are substantiallyinfusible and insoluble. Thermosetting resins are often liquid at somestage in their manufacture or processing, which are cured by heat,catalysis, or some other chemical means. After being fully cured,thermosets cannot be resoftened by heat. Some plastics which arenormally thermoplastic can be made thermosetting by means ofcrosslinking with other materials."

BIS(AMINOPHENOXY)-ALPHA-SUBSTITUTED STILBENE PREPARATION

The bis(aminophenoxy)-alpha-substituted stilbenes of the presentinvention can be prepared by reacting the correspondingdihydroxy-alpha-substituted stilbene compound with a halonitrobenzene inthe presence of a basic acting substance and, optionally, one or moresolvents, to provide the correspondingbis(nitrophenoxy)-alpha-substituted stilbene. The resultantbis(nitrophenoxy)-alpha-substituted stilbene is then hydrogenated toselectively convert the nitro groups to amine groups.

Suitable dihydroxy-alpha-substituted stilbene compounds which can beemployed herein include those represented by the following Formula II##STR3## wherein R, R², X and n are as hereinbefore defined.

Particularly suitable dihydroxy-alpha-substituted stilbene compoundsrepresented by Formula II which can be employed herein to prepare thebis(nitrophenoxy)-alpha-substituted stilbene precursors to thebis(aminophenoxy)-alpha-substituted stilbene compositions of the presentinvention include, for example, 4,4'-dihydroxy-alphamethylstilbene,4,4'-dihydroxy-alpha-ethylstilbene, 4,4'-dihydroxy-alpha-propylstilbene,3,3'-dimethyl-4,4'-dihydroxy-alpha-methylstilbene,3,3',5,5'-tetramethyl-4,4'-dihydroxy-alpha-methylstilbene,2,2'-dihydroxy-alpha-methylstilbene,2,4'-dihydroxy-alpha-methylstilbene,2',4-dihydroxy-alpha-methylstilbene,4,4'-dihydroxy-alpha-chlorostilbene, 4,4'-dihydroxy-alpha-cyanostilbene,3,3'-dicyano-4,4'-dihydroxy-alpha-methylstilbene,3,3'-dichloro-4,4'-dihydroxy-alpha-methylstilbene,3,3'-dibromo-4,4'-dihydroxy-alpha-methylstilbene,3,3'-difluoro-4,4'-dihydroxy-alpha-methylstilbene, or any combinationthereof and the like.

Halonitrobenzenes suitable for use herein contain the halogen atom orthoor para to a nitro group and include, for example, 2-chloronitrobenzene,4-chloronitrobenzene, 2-bromonitrobenzene, 4-bromonitrobenzene,3-methyl-4-chloronitrobenzene, 2-methyl-4-chloronitrobenzene,3,5-dimethyl-4-chloronitrobenzene, 2,6-dimethyl-4-chloronitrobenzene,3,6-dimethyl-4-chloronitrobenzene, 2,5-dimethyl-4-chloronitrobenzene,3-methyl-2-chloronitrobenzene, 3,6-dimethyl-2-chloronitrobenzene,6-methyl-2-chloronitrobenzene, 2-phenyl-4-chloronitrobenzene,4-phenyl-2-chloronitrobenzene, or any combination thereof and the like.The halonitrobenzene is usually employed in amounts which provide fromabout 1.05:1 to about 5:1, more suitably from about 1.10:1 to about 2:1,more suitably from about 1.20:1 to about 1.5:1 equivalents ofhalonitrobenzene per phenolic hydroxyl group. At amounts ofhalonitrobenzene below about 1.05 equivalents per phenolic hydroxylgroup, conversion of the dihydroxy-alpha-substituted stilbene to thecorresponding bis(aminophenoxy)-alpha-substituted stilbene is incompleteor occurs at an undesireably slow rate. Amounts of halonitrobenzeneabove abut 5 equivalents per phenolic hydroxyl group provide an excessdilution of the reaction.

Suitable basic acting substances for use herein to induce formation ofthe bis(phenolate) of the dihydroxy-alpha-substituted stilbene compoundsinclude, for example, the alkali metal or alkaline earth metalhydroxides, carbonates or any combination thereof and the like, such assodium hydroxide, potassium hydroxide, lithium hydroxide, calciumhydroxide, barium hydroxide, magnesium hydroxide, manganese hydroxide,sodium carbonate, potassium carbonate, lithium carbonate, calciumcarbonate, barium carbonate, magnesium carbonate, manganese carbonate,any combination thereof and the like. Most preferred as the basic actingsubstance is potassium carbonate. The basic acting substance is usuallyemployed in amounts which provide from about 1.05:1 to about 2:1, moresuitably from about 1.10:1 to about 1.5:1, more suitably from about1.15:1 to about 1.3:1 equivalents of basic acting substance per phenolichydroxy group. At amounts of basic acting substance below about 1.05equivalents per phenolic hydroxyl group, conversion of thedihydroxy-alpha-substituted stilbene to the correspondingbis(aminophenoxy)-alpha-substituted stilbene is incomplete or occurs atan undesireably slow rate. Amounts of basic acting substance above about2 equivalents per phenolic hydroxyl group provide an excess dilution ofthe reaction.

Suitable solvents which can be employed herein include, for example, anexcess of one or more halonitrobenzenes, aliphatic hydrocarbons,aromatic hydrocarbons, glycol ethers, amides, sulfoxides, sulfones,ethers, mixtures thereof and the like. Particularly suitable solventsinclude, for example, 2,5-dimethylheptane, 4-ethylheptane,2-methyloctane, nonane, decane, toluene, xylene, decahydronaphthalene,ethylene glycol ethyl ether, ethylene glycol n-butyl ether, ethyleneglycol phenyl ether, propylene glycol ethyl ether, propylene glycoln-butyl ether, propylene glycol phenyl ether, diethylene glycol methylether, diethylene glycol ethyl ether, diethylene glycol n-butyl ether,diethylene glycol phenyl ether, tripropylene glycol methyl ether,butylene glycol methyl ether, N,N-dimethylformamide,N-methylpyrrolidinone, N,N-dimethylacetamide, dimethylsulfoxide,sulfolane, di-n-butyl ether, diphenyl ether, 2,5-dimethyl-1,4-dioxane,mixtures thereof and the like. Most preferred as the solvent isN,N-dimethylformamide. The solvent is usually employed in amounts ofsuitably from zero to about 95, more suitably from about 10 to about 80,more suitably from about 20 to about 70, percent by weight based on thecombined weight of solvent and reactants. Larger amounts of solventprovide an excess dilution of the reaction.

The reaction to form the bis(nitrophenoxy)-alpha-substituted stilbeneprecursor to the bis(aminophenoxy)-alpha-substituted stilbenecompositions of the present invention can be conducted at atmospheric,superatmospheric or subatmospheric pressures at temperatures of fromabout 80 deg. C. to about 175 deg. C., preferably from about 100 deg. C.to about 160 deg. C., more preferably from about 125 deg. C. to about150 deg C. The time required to complete the reaction depends upon thetemperature, reactants and solvent, if any, employed. Highertemperatures require shorter periods of time whereas longer temperaturesrequire longer periods of time. Generally, however, times of from aboutthirty minutes to about 96 hours, preferably from about one hour toabout 24 hours, more preferably from about 3 hours to about 12 hours aresuitable. At temperatures below about 80 deg. C. conversion of thedihydroxy-alpha-substituted stilbene to the correspondingbis(aminophenoxy)-alpha-substituted stilbene is incomplete or occurs atan undesireably slow rate. At temperatures above about 175 deg. C.excessive discoloration or even decomposition of the product occurs.

The resultant bis(nitrophenoxy)-alpha-substituted stilbene precursor tothe bis(aminophenoxy)-alpha-substituted stilbene is hydrogenated usingmethods well known to the skilled artisan. Thus suitable such methodsfor the reduction of nitro compounds to amines are disclosed by March inAdvanced Organic Chemistry, John Wiley and Sons, pages 1103 to 1106(1985). The general methods cited therein for the reduction reactioninclude the use of iron, zinc or tin plus a mineral acid, catalytichydrogenation, for example in the presence of platinum, AlH₃ -AlCl₃,hydrazine plus catalyst, dodecacarbonyltriiron-methanol, TiCl₃, hotliquid paraffin, formic acid and palladium on carbon, sulfides such asNaHS, and sodium dihydro(trithio)borate. For the reduction of the nitrogroup in the presence of the unsaturated alpha-substituted stilbenemoiety, a functional group also susceptible to reduction, certain of thereduction chemistries are preferred. Thus, catalytic reduction usingRaney nickel, aqueous ferrous sulfate heptahydrate and ammoniumhydroxide, aqueous sodium hydrosulfite and potassium carbonate solution,or powdered zinc in ammonium hydroxide are preferred. Details concerningthe three latter aforementioned reduction methods are provided in U.S.Pat. Nos. 3,845,018 and 3,975,444, both of which are incorporated hereinby reference in their entirety.

The reduction using catalytic Raney nickel is usually conducted in aninert solvent at superatmospheric hydrogen pressures at a temperature offrom about 10 deg. C. to about 150 deg. C., preferably from about 20deg. C. to about 50 deg. C. The time required to complete the reactiondepends upon the temperature, the specificbis(nitrophenoxy)-alpha-substituted stilbene reactant, the amount ofcatalyst and the solvent employed. Higher temperatures require shorterperiods of time whereas longer temperatures require longer periods oftime. Generally, however, times of from about 5 minutes to about 24hours, preferably from about 15 minutes to about 12 hours are suitable.Solvents which can be employed in the hydrogenation include aliphaticalcohols, such as, for example, methanol, ethanol, isopropanol;aliphatic carboxylic acid esters, such as, for example, ethyl acetate;aliphatic or cycloaliphatic ethers and diethers, such as, for example,diethylether, 1,4-dioxane, 2,5-dimethyl-1,4-dioxane; mixtures thereofand the like.

When chemistry to incorporate certain aryl substitutuents into thebis(aminophenoxy)-alpha-substituted stilbene compositions (Formula Iwhere at least one R is other than hydrogen) is to be practiced, it isfrequently of value to protect the amine functionalities prior to thesubstitution reaction followed by deprotection to regenerate the freeamine groups. General methodology for the protection-deprotection of theamine group is well established, for example, as reported by T. W.Greene and P. G. M. Wuts in Protective Groups in Organic Synthesispublished by John Wiley and Sons, Inc., New York (1991) on pages309-405. One of the methods cited therein is protection-deprotection ofthe amine group via formation of the carbamate group. As a specificexample of this method, the amine group is protected via reaction withmethyl chloroformate at reflux for 12 hours in the presence of potassiumcarbonate as the hydrochloric acid acceptor. Deprotection (cleavage tothe amine group) is accomplished via reaction of the carbamate groupwith potassium hydroxide, water, ethylene glycol at 100 deg. C. for 12hours, or by reaction of the carbamate group with hydrobromic acid,acetic acid at 25 deg. C. for 18 hours, or by the reaction of thecarbamate group with lithium n-propyl mercaptide at 0 deg. C. for 8.5hours. A second method cited in the Greene and Wuts reference isprotection-deprotection of the amine group via formation of the amidegroup. As a specific example of this method, the amine group isprotected via reaction with trifluoroacetic acid ethyl ester,triethylamine, methanol at 25 deg. C. for 15 to 45 hours. Deprotectionis accomplished via reaction of the trifluoroacetamide group withpotassium carbonate, methanol, water at 25 deg. C. or by reaction of thetrifluoroacetamide group with ammonia in methanol or by the reaction ofthe trifluoroacetamide group with 0.2N barium hydroxide in methanol at25 deg. C. for 2 hours. A third example cited in the Greene and Wutsreference is protection-deprotection of the amime group via formation ofthe imine group. As a specific example of this method, the amine groupis protected via reaction with benzaldehyde in benzene at 25 deg. C. inthe presence of sodium sulfite present is the dessicant. Deprotection isaccomplished via reaction of the N-benzylideneamine group with 1Nhydrochloric acid at 25 deg. C. for one hour or by the reaction of theN-benzylideneamine group with hydrazine in ethanol at reflux for 6hours. Protection-deprotection is usually desireable only if arylsubstitutent(s) are present in the correspondingdihydroxy-alpha-substituted stilbene precursor (Formula II where atleast one R is other than hydrogen) which would not survive theaforementioned conditions required for the reactions leading to thebis(aminophenoxy)-alpha-substituted stilbene compositions of the presentinvention and which cannot themselves be protected then deprotected.

Methods for use in preparing N-substitutedbis(aminophenoxy)-alpha-substituted stilbene compositions (Formula Iwhere at least one R¹ is other than hydrogen) can be adapted from thetechniques given by Sandler and Karo in Organic Functional GroupPreparations published by Academic Press, Inc., New York (1983) on pages387-390. In the general method, the bis(aminophenoxy)-alpha-substitutedstilbene is converted to the correspondingbis(acetamidophenoxy)-alpha-substituted stilbene followed byN-alkylation to provide the correspondingN,N'-dialkyl-bis(acetamidophenoxy)-alpha-substituted stilbene.Hydrolyric cleavage of the acetamido group provides the desiredN,N'-dialkyl-bis(aminophenoxy)-alpha-substituted stilbene. An additionalmethod for use in preparing the N-substitutedbis(aminophenoxy)-alpha-substituted stilbene compositions may be adaptedfrom the technique given by Allen and VanAllan in Organic SynthesisCollective Volume III (E. C. Homing (ed.)) published by John Wiley andSons, Inc., New York (1965 printing) on pages 827-828. In the generalmethod, the bis(aminophenoxy)-alpha-substituted stilbene is reacted witha primary alkylaldehyde (cycloaliphatic aldehyde, benzaldehyde) toprovide the corresponding imino compound. Hydrogenation, for exampleusing hydrogen with Raney nickel catalyst, of the imino compoundprovides the desired N,N'-dialkyl-bis(aminophenoxy)-alpha-substitutedstilbene.

EPOXY RESINS

The epoxy resins which can be employed to prepare the curablecompositions of the present invention include essentially anyepoxy-containing compound which contains an average of more than onevicinal epoxide group per molecule. The epoxide groups can be attachedto any oxygen, sulfur or nitrogen atom or the single bonded oxygen atomattached to the carbon atom of a --CO--O-- group in which said oxygen,sulfur or nitrogen atom or the carbon atom of the --CO--O-- group isattached to an aliphatic, cycloaliphatic, polycycloaliphatic or aromatichydrocarbon group which hydrocarbon group can be substituted with anyinert substituent including, but not limited to, halogen atoms,preferably fluorine, bromine or chlorine, nitro groups, and the like orsuch groups can be attached to the terminal carbon atoms of a compoundcontaining an average of more than one --(O--CHR^(a) --CHR^(a))_(t) --group where each R^(a) is independently hydrogen or an alkyl orhaloalkyl group, containing from one to about 2 carbon atoms, with theproviso that only one R^(a) group can be a haloalkyl group, and t has avalue from one to about 100, preferably from one to about 20, morepreferably from one to about 10, most preferably from one to about 5.

Suitable such epoxy resins which can be combined with thebis(aminophenoxy)-alpha-substituted stilbene compositions to prepare thecurable compositions of the present invention include, for example, theglycidyl ethers or glycidyl amines represented by the following FormulasIII, IV, V, VI, VII, VIII, IX, X or XI ##STR4## wherein R and n are ashereinbefore defined; each A is independently a direct single bond, adivalent hydrocarbyl group having from one to about 20, preferably fromone to about 6, carbon atoms, --O--, --CO--, --SO--, --SO₂ --, --S--,--S--S--, --CR⁷ ═CR⁷ --, --C.tbd.C--, --N═--, --CR⁷ ═N--, --M═CR⁷ --,--O--CO--, --CO--O--, --S--CO--, --CO--S--, --NR⁷ --CO--, --CO--NR⁷ --,--CR⁷ ═N--N═CR⁷ --, --CO--CR⁷ ═CR⁷ --, --CR⁷ ═CR⁷ --CO--, --CO--O--N═CR⁷--, --CR⁷ ═N--O--OC--, --CO--O--N═CR⁷ --, --CO--NR⁷ --NR⁷ --OC--, --CR⁷═CR⁷ --O--OC--, --CO--O--CR⁷ ═CR⁷ --, --O-- CO--CR⁷ ═CR⁷ --, --CR⁷ ═CR⁷--CO--O--, --(CHR⁷)_(n), --O--CO--CR⁷ ═CR⁷ --, --CR⁷ ═CR⁷--CO--O--(CHR⁷)_(n') --, --(CHR⁷)_(n') --CO--O--CR⁷ ═CR⁷, --CR⁷ ═CR⁷--O--CO--(CHR⁷)n'--, --CH₂ --CH₂ --CO--O--, --O--OC--CH₂ --CH₂ --,--C.tbd.C--C.tbd.C--, --CR⁷ ═CR⁷ --CR⁷ ═CR⁷ --, --CR⁷ ═CR⁷ --C.tbd.C--,--C.tbd.C--CR⁷ ═CR⁷ --, --CR⁷ ═CR⁷ --CH₂ --O--OC--, --CO--O--CH₂ --CR⁷═CR⁷ --, --O--CO--C.tbd.C--CO--O--, --O--CO--CR⁷ ═CR⁷ --CO--O--,--O--CO--CH₂ --CH₂ --CO--O--, --S--CO-- CR⁷ ═CR⁷ --CO--S--, --CO--CH₂--NH--CO--, --CO--NH--CH₂ --CO--, --NH--C(--CH₃)═CH--CO--,--CO--CH═C(--CH₃)--NH--, --CR⁷ ═C(--Cl)--, --C()--Cl)═CR⁷ --, --CR⁷═C(--CN)--, --C(--CN)═CR⁷ --, --N═C(--CN)--, --C(--CN)═N--, --CR⁷═C(--CN)--CO--O--, --O--CO--C(--CN)═CR⁷ --, ##STR5## each A' isindependently a divalent hydrocarbyl group having from one to about 10,preferably from 1 to about 6, more preferably from one to about 2,carbon atoms; A" is a divalent hydrocarbyl group having from one toabout 6, preferably from one to about 4, more preferably from one toabout 2, carbon atoms; each A¹ is independently a --CO--, --O--CO--,--CO--O--, --CO--S--, --S--CO--, --CO--NR⁷ -- or --NR⁷ --CO--; each R⁴is independently hydrogen or a hydrocarbyl group having from one toabout 3 carbon atoms; each R⁵ is independently hydrogen, a hydrocarbylgroup having from one to about 10, preferably from one to about 6, morepreferably from one to about 3, carbon atoms or a halogen atom,preferably chlorine or bromine; each R⁶ is independently hydrogen or ahydrocarbyl or halohydrocarbyl group having from one to about 6,preferably from 1 to about 4, more preferably from one to about 2 carbonatoms; Q is a direct bond, --CH₂ --S--CH₂ --, --(CH₂)_(n") --, or##STR6## each R⁷ is independently hydrogen or a hydrocarbyl group havingfrom one to about 6, preferably from one to about 4, more preferablyfrom one to about 2, carbon atoms, and is preferably hydrogen or ahydrocarbyl group containing one carbon atom; each R⁸ is independently ahydrocarbyl group having from 1 to about 10, preferably from 1 to about6, more preferably ##STR7## from 1 to about 2, carbon atoms or a group;m has a value from about 0,001 to about 6, preferably from about 0.01 toabout 3; m' has a value from one to about 10, preferably from one toabout 4; n' has a value of one or two, n" has an average value of fromabout one to about 10; p has a value from zero to about 30, preferablyfrom zero to about 5 and p¹ has a value of from one to about 30,preferably from one to about 3. The aromatic rings in Formulas III, IV,V, VI, VII, VIII, X and XI can also contain one or more heteroatomsselected from N, O, and S. The term "hydrocarbyl", when applied to theA" group of Formula VIII, can also include one or more heteroatomsselected from N, O and S. Thus, A" may be, for example, the --CO-- or--CH₂ --O--CH.sub. 2 -- group.

Mesogenic epoxy resins include those represented by Formulas IV, VII,VIII and XI wherein each A is independently selected from theaforementioned listing, but with the proviso that A may not be adivalent hydrocarbyl group having from one to 20 carbon atoms, --O--,--CO--, --SO--, --SO₂ --, --S--, --S--S-- and with the proviso that atleast 80 percent of the molecules are para substituted by the bridginggroups (--A--) in Formulas IV, VII, XI and by the direct bond in FormulaVIII, the substituent containing the glycidyl, ##STR8## group(s), andthe substituent containing the secondary hydroxyalkylidene, --CH₂--C(OH)(R⁴)--CH₂ --, group(s) which are present when p or p¹ has a valuegreater than zero.

Representative epoxy resins include, for example, the diglycidyl ethersof: resorcinol, hydroquinone, 4,4'-isopropylidenediphenol (bisphenol A),4,4'-dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxybenzophenone,3,3'5,5'-tetrabromo-4,4'-isopropylidenediphenol, 4,4'-thiodiphenol,4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,1,1-bis(4-hydroxyphenyl)-1-phenylethane,3,3',5,5'-tetrachloro-4,4'-isopropylidenediphenol A,3,3'-dimethoxy-4,4'-isopropylidenediphenol,4,4'-dihydroxy-alpha-methylstilbene, 4,4'-dihydroxybenzanilide,4,4'-dihydroxyazoxybenzene, 4,4'-dihydroxybiphenyl,4,4'-dihydroxydiphenylazomethine, 4,4'-dihydroxydiphenylacetylene,4,4'-dihydroxystilbene, 4,4'-dihydroxy-alpha-cyanostilbene,4,4'-dihydroxyazobenzene, 4,4'-dihydroxyazoxybenzene,4,4'-dihydroxychalcone, 4-hydroxyphenyl-4-hydroxybenzoate; dipropyleneglycol, poly(propylene glycol), thiodiglycol; the triglycidyl ether oftris(hydroxyphenyl)methane; the polyglycidyl ethers of a phenol or alkylor halogen substituted phenol-aldehyde acid catalyzed condensationproduct (novolac resins); the tetraglycidyl amines of:4,4'-diaminodiphenylmethane, 4,4'-diaminostilbene,N,N'-dimethyl-4,4'-diaminostilbene, 4,4'-diaminobenzanilide,4,4'-diaminobiphenyl, 4,4'-diamino-alphamethylstilbene; the polyglycidylether of the condensation product of: a dicyclopentadiene or an oligomerthereof and a phenol or alkyl or halogen substituted phenol; theadvancement reaction products of the aforesaid di and polyglycidylethers with aromatic di and polyhydroxyl or carboxylic acid containingcompounds including, for example, hydroquinone, resorcinol, catechol,2,4-dimethylresorcinol, 4-chlororesorcinol, tetramethylhydroquinone,4,4'-isopropylidenediphenol (bisphenol A), 4,4'dihydroxydiphenylmethane,4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 2,2'-sulfonyldiphenol,4,4'-dihydroxydiphenyl oxide, 4,4'-dihydroxybenzophenone,1,1-bis(4-hydroxyphenyl)-1-phenylethane,4,4'-bis(4(4-hydroxyphenoxy)-phenylsulfone)diphenyl ether,4,4'-dihydroxydiphenyl disulfide,3,3',3,5'-tetrachloro-4,4'-isopropylidenediphenol,3,3',3,5'-tetrabromo-4,4'-isopropylidenediphenol,3,3'-dimethoxy-4,4'-isopropylidenediphenol, 4,4'-dihydroxybiphenyl,4,4'-dihydroxy-alpha-methylstilbene, 4,4'-dihydroxybenzanilide,bis(4-hydroxyphenyl)terephthalate,N,N'-bis(4-hydroxyphenyl)terephthalamide,bis(4'-hydroxybiphenyl)terephthalate, 4,4'-dihydroxyphenylbenzoate,bis(4'-hydroxyphenyl)-1,4-benzenediimine;1,1'-bis(4-hydroxyphenyl)cyclohexane, phloroglucinol, pyrogallol,2,2',5,5'-tetrahydroxydiphenyl sulfone, tris(hydroxyphenyl)methane,dicyclopentadiene diphenol, tricyclopentadiene diphenol, terephthalicacid, isophthalic acid, 4,4'-benzanilidedicarboxylic acid,4,4'-phenylbenzoatedicarboxylic acid, 4,4'-stilbenedicarboxylic acid,adipic acid; or any combination of the aforementioned epoxy resins andthe like.

These epoxy resins can be prepared generally by reacting a di- orpolyhydroxyl containing compound with an epihalohydrin in the presenceof a suitable catalyst and in the presence or absence of a suitablesolvent at a temperature suitably from about 0 deg. C. to about 100 deg.C., more suitably from about 20 deg. C. to about 80 deg C., mostsuitably from about 20 deg. C. to about 65 deg. C.; at pressuressuitably from about 30 mm Hg vacuum to about 100 psia., more suitablyfrom about 30 Hg vacuum to about 50 psia., most suitably from about 60mm Hg vacuum to about atmospheric pressure; for a time sufficient tocomplete the reaction, usually from about 0.5 to about 24, more usuallyfrom about 1 to about 12, most usually from about 1 to about 8 hours;and using from about 1.5:1 to 100:1, preferably from about 2:1 to about50:1, most preferably from about 3:1 to about 20:1 moles ofepihalohydrin per hydroxyl group. This initial reaction, unless thecatalyst is an alkali metal or alkaline earth metal hydroxide employedin stoichiometric quantities, produces a halohydrin intermediate whichis then reacted with a basic acting substance to convert the vicinalhalohydrin groups to epoxide groups. The resultant product is a glycidylether compound.

Advancement reaction of di- and polyglycidyl ethers can be performed bythe known methods which usually includes combining one or more suitablecompounds having an average of more than one active hydrogen atom permolecule, including, for example, dihydroxy aromatic, dithiol ordicarboxylic acid compounds or compounds containing one primary amine oramide group or two secondary amine groups and the di- or polyglycidylethers in the presence or absence of a suitable solvent with theapplication of heat and mixing to effect the advancement reaction. Theepoxy resin and the compound having more than one active hydrogen atomper molecule are reacted in amounts which provide suitably from abut0.01:1 to about 0.95:1, more suitably from about 0.05:1 to about 0.8:1,most suitably from about 0.10:1 to about 0.5:1 active hydrogen atoms perepoxy group. The advancement reaction can be conducted at atmospheric,superatmospheric or subatmospheric pressures at temperatures of fromabout 20 deg. C. to about 260 deg. C., more suitably from about 80 deg.C. to about 240 deg. C., most suitably from about 100 deg. C. to about200 deg. C. The time required to complete the advancement reactiondepends upon the temperature employed. Higher temperatures requireshorter periods of time whereas lower temperatures require longerperiods of time. Generally, times of from about 5 minutes to about 24hours, more suitably from about 30 minutes to about 8 hours, mostsuitably from about 30 minutes to about 4 hours are employed. Acatalyst, including, for example, phosphines, quaternary ammoniumcompounds, phosphonium compounds and tertiary amines, is frequentlyadded to facilitate the advancement reaction and is usually employed inquantities of from about 0.01 to about 3, preferably from about 0.03 toabout 1.5, most preferably from about 0.05 to about 1.5 percent byweight based upon the weight of the epoxy resin.

CURING AGENTS, CURING CATALYSTS AND CURABLE BLENDS

The curable compositions of the present invention are prepared by mixingtogether one or more of the bis(aminophenoxy)-alpha-substituted stilbenecompositions with one or more epoxy resins and/or advanced epoxy resins,which all, none or a part of said epoxy resins and/or advanced epoxyresins may contain one or more mesogenic moities. Thebis(aminophenoxy)-alpha-substituted stilbene compositions are employedin amounts which will effectively cure the mixture, with theunderstanding that the these amounts will depend upon the particularbis(aminophenoxy)-alpha-substituted stilbene and epoxy resin employed.Generally, suitable amounts are from about 0.80:1 to abut 1.50:1,preferably from abut 0.95:1 to abut 1.05:1 equivalents of amine hydrogenin the bis(aminophenoxy)-alpha-substituted stilbene which is reactivewith an epoxide group per equivalent of epoxide group in the epoxy resinat the conditions employed for curing.

The curing of the curable compositions of the present invention can beconducted at atmospheric, superatmospheric or subatmospheric pressuresat temperatures of from about 0 deg. C. to about 300 deg. C., preferablyfrom about 50 deg. C. to about 240 deg. C., more preferably from about100 deg. C. to about 200 deg. C. The time required to complete curingdepends upon the temperature employed. Higher temperatures requireshorter periods of time whereas lower temperatures require longerperiods of time. Generally, however, times of from about one minute toabout 48 hours, preferably from about 15 minutes to about 8 hours, morepreferably from about 30 minutes to about 3 hours are suitable.

It is also operable to partially cure (B-stage) the curable compositionsof the present invention and then complete the curing at a later time.B-staging (partial cure) can be accomplished by heating at a temperaturefor a time such that only partial curing is produced. Usually, the curetemperatures are employed for B-staging; however for a shorter period oftime. Generally, the extent of B-staging is monitored using analyticalmethods such as viscosity measurement, differential scanning calorimetryfor residual cure energy or infrared spectrophotometric analysis forunreacted curable functional groups.

A preferred curable mixture of the present invention comprises a curingamount of one or more 4,4'-bis(4-aminophenoxy)-alpha-alkylstilbenes orN,N'-dialkyl-4,4'-bis(4-aminophenoxy)-alphaalkylstilbenes with one ormore epoxy resins containing one or more mesogenic moieties. Anadditional preferred curable mixture of the present invention comprisesa curing amount of one or more4,4'-bis(2-aminophenoxy)-alpha-alkylstilbenes orN,N'-dialkyl-4,4'-bis(2-aminophenoxy)-alpha-alkylstilbenes with one ormore epoxy resins containing one or more mesogenic moieties. A likewisepreferred curable mixture of the present invention comprises a curingamount of a combination of one or more4,4'-bis(4-aminophenoxy)-alphaalkylstilbenes orN,N'-dialkyl-4,4'-bis(4-aminophenoxy)-alphaalkylstilbenes and one ormore 4,4'-bis(2-aminophenoxy)-alphaalkylstilbenes orN,N'-dialkyl-4,4'-bis(2-aminophenoxy)-alphaalkylstilbenes with one ormore epoxy resins containing one or more mesogenic moieties. Mostpreferred as the curable mixtures of the present invention are each ofthe aforementioned curable mixtures wherein saidbis(aminophenoxy)-alpha-alkylstilbene and/orN,N'-dialkyl-bis(aminophenoxy)-alpha-alkylstilbene is thealphamethylstilbene compound and the N,N'-dimethyl-alpha-methylstilbenecompound, respectively, and the epoxy resin is the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene.

The curable mixtures of the present invention may also contain one ormore of the known conventional curing agents and/or catalysts for curingepoxy resins, such as, for example, aliphatic, cycloaliphatic,polycycloaliphatic or aromatic primary monoamines; aliphatic,cycloaliphatic, polycycloaliphatic or aromatic primary and secondarypolyamines; carboxylic acids and anhydrides thereof; aromatic hydroxylcontaining compounds; imidazoles; guanidines; ureaaldehyde resins;melamine-aldehyde resins; alkoxylated urea-aldehyde resins; alkoxylatedmelamine-aldehyde resins; amidoamines; epoxy resin adducts all, none, ora part of which may contain one or more mesogenic moieties; combinationsthereof and the like. Particularly suitable curing agents include, forexample, methylenedianiline, 4,4'-diaminostilbene,4,4'-diamino-alpha-methylstilbene, 4,4'-diaminobenzanilide,dicyandiamide, ethylene diamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, urea-formaldehyde resins,melamine-formaldehyde resins, methylolated urea-formaldehyde resins,methylolated melamine-formaldehyde resins, phenol-formaldehyde novolacresins, cresol-formaldehyde novolac resins, sulfanilamide,diaminodiphenylsulfone, diethyltoluenediamine, t-butyltoluenediamine,bis-4-aminocyclohexylamine, isophoronediamine, diaminocyclohexane,hexamethylenediamine, piperazine, aminoethylpiperazine,2,5-dimethyl-2,5-hexanediamine, 1,12-dodecanediamine,tris-3-aminopropylamine, combinations thereof and the like. If used acomponent of the curable mixtures of the present invention, from about 1to about 99, preferably from abut 1 to about 40, most preferably fromabout 1 to abut 20 percent of the equivalents of amine hydrogen whichare reactive with an epoxide group provided by thebis(aminophenoxy)-alpha-substituted stilbene are substituted using oneor more of the aforesaid curing agents. This substitution is on anequivalent basis.

Particularly suitable curing catalysts include boron trifluoride, borontrifluoride etherate, aluminum chloride, ferric chloride, zinc chloride,silicon tetrachloride, stannic chloride, titanium tetrachloride,antimony trichloride, boron trifluoride monoethanolamine complex, borontrifluoride triethanolamine complex, boron trifluoride piperidinecomplex, pyridine-borane complex, diethanolamine borate, zincfluoroborate, mixtures thereof and the like.

The curing catalysts are employed in amounts which will effectively curethe curable composition, however, these amounts will depend upon theparticular bis(aminophenoxy)-alpha-substituted stilbene employed and theepoxy resin employed. Generally suitable amounts include, for example,0.001 to about 2 percent by weight of the total epoxy resin used. It isfrequently of benefit to employ one or more of the curing catalysts inthe curing of the curable compositions of the present invention. This isgenerally done to accelerate or otherwise modify the curing behaviorobtained when a curing catalyst is not used.

For the curable blends of one or morebis(aminophenoxy)-alpha-substituted stilbenes and one or more epoxyresins and/or advanced epoxy resins, when mesogenic moieties are presentin one or more components of said blends other than thebis(aminophenoxy)-alpha-substituted stilbenes, it is frequently of valueto B-stage the curable blend in order to chain extend the resin. Thischain extension is required for some mesogen containing curable blendsin order to achieve liquid crystal character. B-staging can also beemployed to increase the temperature range at which a particular curableblend is liquid crystalline and to control the degree of crosslinkingduring the final curing stage.

ORIENTATION

For the curable blends of one or morebis(aminophenoxy)-alpha-substituted stilbenes and one or more epoxyresins and/or advanced epoxy resins, when mesogenic moieties are presentin one or more components of said blends, before and/or duringprocessing and/or curing into a part, electric or magnetic fields,drawing and/or shear stresses can be applied for the purpose oforienting the liquid crystal moleties contained or developed thereinwhich in effect improves the mechanical properties. As specific examplesof these methods, Finkelmann, et al, Macromol. Chem., volume 180, pages803-806 (March, 1979) induced orientation in thermotropic thermoplasticmethacrylate copolymers containing mesogenic side chain groups decoupledfrom the main chain via flexible spacers in an electric field. Withinthe nematic liquid crystalline transition temperature range for one ofthe copolymers, homeotropic orientation was achieved with a half-time ofapproximately 10 seconds at 8 volts d.c. At higher voltages, turbulentflow disrupted the homeotropic orientation. A second copolymer withinthe nematic liquid crystalline transition temperature range gavereversible homeotropic orientation with an orientation time of less than200 mseconds in a 50 Hz d.c. electric field. Threshold voltage wasapproximately 6 volts and the relaxation half-time was approximately 5seconds. Thus, for the orientation of the curable blends of the presentinvention which contain or develop liquid crystal moieties, it isfrequently of value to conduct simple preliminary experiments over therange of experimental conditions to be employed, including voltage to beapplied and time to be used for application of the voltage to a givenmesophase at a given temperature. In this manner, an indication of thecritical electric field strength, orientation time and relaxation timefor the mesophase to be oriented can be obtained and conditions notconducive to orientation, such as flow instability, can be avoided.Orientation of mesogenic side chain groups decoupled from thethermoplastic polymer main chain via flexible spacers in a magneticfield has been demonstrated by Roth and Kruecke, Macromol. Chem., volume187, pages 2655-2662 (November, 1986). Within the broad temperaturerange of approximately -120 deg. C. to 200 deg. C., orientation of thepolymers was observed (anisotropy in the motional processes as shown bychange in line width of proton magnetic resonance signals as a functionof temperature). In order to achieve macroscopic orientation in amagnetic field of abut 2T it was found that the choice of propertemperature is important such that the ordering effect of the magneticfield overcomes the disordering effect of thermal motion and thatsufficient molecular mobility is present to allow for the ordering tooccur. Furthermore, this proper temperature was found to vary as afunction of the particular mesogen-containing polymer to be oriented.Thus, for the orientation of the curable blends of the present inventionwhich contain or develop liquid crystal moieties, it is frequently ofvalue to conduct simple preliminary experiments over the range ofexperimental conditions to be employed, including the magnetic field tobe applied and time to be used for application of the magnetic field toa given mesophase at a given temperature. In this manner, an indicationof the critical magnetic field strength, orientation time and relaxationtime for the mesophase to be oriented can be obtained and conditions notconducive to orientation, such as improper temperature range, can beavoided. Magnetic field induced orientation of mesogenic main chaincontaining thermoplastic polymers has been demonstrated by Moore, et al,ACS Polymeric Materials Sciences and Engineering, volume 52, pages 84-86(Apr.-May, 1985). At the melt temperature for the liquid crystallinethermoplastic copolymer of p-hydroxybenzoic acid (80%) and polyethyleneterephthalate (20%) the threshold for orientation was found to beapproximately 0.4T, with the degree of orientation (order parameter)depending on the strength of the magnetic field. Relaxation of theorientation once the polymer is removed from the magnetic field dependson the amount of time that the polymer spent in the magnetic field.Thus, for the liquid crystalline thermoplastic polymer maintained in a6.3T magnetic field, maximum relaxation time was approximately 15minutes, while the liquid crystalline thermoplastic polymer maintainedin a 2T or less magnetic field exhibited a maximum relaxation time ofless than one minute. An equation delineating the balance between theordering effect of the magnetic field and the disordering effect ofthermal motion is given for domains of radius a as follows:

    X.sub.a ·H.sub.t.sup.2 ·a.sup.2 =kT/a

where H_(t) is the threshold magnetic field and X_(a) is the differencebetween the magnetic susceptibilities of the polymer when alignedparallel and perpendicular to the field. Magnetic and electric fieldorientation of low molecular weight mesogenic compounds is discussed byW. R. Krigbaum in Polymer Liquid Crystals, pages 275-309 (1982)published by Academic Press, Inc.

In addition to orientation by electric or magnetic fields, polymericmesophases can be oriented by shear forces, for example, using shearrates as low as 0.1 sec⁻¹ to as high as 10,000 sec⁻¹, which are inducedby drawing and/or flow through dies, orifices and mold gates. A generaldiscussion for orientation of thermotropic liquid crystal polymers bythis method is given by S. K. Garg and S. Kenig in High ModulusPolymers, pages 71-103 (1988) published by Marcel Dekker, Inc. and S.Keneg, Polymer Engineering and Science, volume 29, number 16, pages1136-1141 (August, 1989). For the orientation by shear forces of thecurable blends of the present invention which contain or develop liquidcrystal moieties, it is frequently of value to conduct simplepreliminary experiments over the range of experimental conditions to beemployed, including total shear strain to be applied and time to be usedfor application of the shear force to a given mesophase at a giventemperature. In this manner, an indication of the critical total shearstrain, orientation time and relaxation time for the mesophase to beoriented can be obtained and conditions not conducive to orientation,such as tumbling of domain structure, can be avoided. For themesomorphic systems based on the curable blends of one or morebis(aminophenoxy)-alpha-substituted stilbenes and one or more epoxyresins and/or advanced epoxy resins, this shear orientation can beproduced by processing methods such as injection molding, extrusion,pultrusion, filament. winding, filming and prepreging.

OTHER COMPONENTS

The curable blends of one or more bis(aminophenoxy)-alpha-substitutedstilbenes and one or more epoxy resins and/or advanced epoxy resins, canbe blended with other materials such as solvents or diluents, fillers,pigments, dyes, flow modifiers, thickeners, reinforcing agents, moldrelease agents, wetting agents, stabilizers, fire retardant agents,surfactants or any combination thereof and the like.

These additives are added in functionally equivalent amounts, e.g., thepigments and/or dyes are added in quantities which will provide thecomposition with the desired color; however, they are suitably employedin amounts of from about zero to about 20, more suitably from about 0.5to about 5, most suitably from about 0.5 to about 3 percent by weightbased upon the weight of the total blended compositions.

Solvents or diluents which can be employed herein include, for example,hydrocarbons, ketones, glycol ethers, aliphatic ethers, cyclic ethers,esters, amides, combinations thereof and the like. Particularly suitablesolvents or diluents include, for example, toluene, xylene,methylethylketone, methylisobutylketone, diethylene glycol methyl ether,dipropylene glycol methyl ether, dimethylformamide,N-methylpyrrolidinone, tetrahydrofuran, dioxane, propylene glycol methylether or any combination thereof and the like.

The modifiers such as thickeners, flow modifiers and the like can besuitably employed in amounts of from zero to about 10, more suitablyfrom about 0.5 to about 6, most suitably from about 0.5 to about 4percent by weight based upon the weight of the total composition.

Reinforcing materials which can be employed herein include natural andsynthetic fibers in the form of woven fabric, mats, monofilament,multifilament, unidirectional fibers, rovings, random fibers orfilaments, inorganic fillers or whiskers, hollow spheres, and the like.Suitable reinforcing materials include glass, ceramics, nylon, rayon,cotton, aramid, graphite, polyalkylene terephthalates, polyethylene,polypropylene, polyesters or any combination thereof and the like.

Suitable fillers which can be employed herein include, for example,inorganic oxides, ceramic microspheres, plastic microspheres, glassmicrospheres, inorganic whiskers, calcium carbonate or any combinationthereof and the like.

The fillers can be employed in amounts suitably from about zero to about95, more suitably from about 10 to about 80, most suitably from about 40to about 60 percent by weight based upon the weight of the totalcomposition.

The curable blends of one or more bis(aminophenoxy)-alpha-substitutedstilbenes and one or more epoxy resins and/or advanced epoxy resins ofthe present invention can be employed in coating, casting,encapsulation, electronic or structural laminate or composite, filamentwinding, molding, and the like applications.

The following examples are illustrative of the present invention, butare not to be construed as to limiting its scope in any manner.

EXAMPLE 1 A. Synthesis of 4,4'-Dihydroxy-alpha-methylstilbene

Phenol (1882 grams, 20.0 moles), chloroacetone (383.7 grams, 4.0 molesas chloroacetone) and methylene chloride (1.8 liters) are added to a 5liter glass reactor equipped with a chilled water condenser, mechanicalstirrer, nitrogen purge (one liter per minute), thermometer, droppingfunnel and jacket for circulating coolant over the reactor exterior.Stirring commences concurrent with cooling of the reactant solution to-10 deg. C. The chloroacetone used is a commercial grade containing96.5% chloroacetone, 2.85% 1,1-dichloroacetone, 0.60% mesityl oxide and0.05% acetone. Concentrated sulfuric acid (392.3 grams, 4.0 moles) isadded to the dropping funnel, then dropwise addition to the stirredreactant solution commences over a three hour period and so as tomaintain the reaction temperature between -10 deg. C. and -12 deg. C.After 16 hours of post reaction at -10 deg. C. to -12 deg. C., theopaque, pale pink colored product is recovered and divided equally intothree 2 liter glass spearatory funnels. The contents of each separatoryfunnel are washed four times each with 500 milliliter portions ofdeionized water. The combined organic layers are recovered and dividedequally into a pair of 4 liter glass beakers. The contents of eachbeaker is stirred, ethanol (400 milliliters) is added, deionized water(250 milliliters) is added and heating commences. Once a temperature of70 deg. C. is achieved and substantially all of the methylene chloridesolvent has boiled off, heating ceases and deionized water is added toeach beaker in an amount sufficient to produce a total volume of 3.8liters. Stirring is maintained for the next 6 hours during which time acrystalline slurry forms in each beaker. At this time, stirring isstopped and the crystalline slurry is chilled to 5 deg. C. and heldtherein for 14 hours. The crystalline product is recovered viafiltration of the chilled crystalline slurry then added to a glassbeaker and combined therein with deionized water (one liter). Stirringand heating commence until the stirred slurry reaches 100 deg. C. After15 minutes at 100 deg. C., the stirred slurry is filtered through afritted glass filter. The product recovered from the filter is dried ina vacuum oven at 80 deg. C. and one mm Hg to a constant weight of 549.7grams of pale pink colored crystalline product. Proton magneticresonance spectroscopy, Fourier transform infrared spectrophotometricanalysis and high pressure liquid chromatography-mass spectrometryconfirm the product structure.

B. Synthesis and Characterization of4,4'-bis(4-Nitrophenoxy)-alpha-methystibene

4,4'-Dihydroxy-alpha-methylstilbene (11.3 grams, 0.10 hydroxylequivalent) from B above, p-chloronitrobenzene (18.9 grams, 0.12 mole),-325 mesh anhydrous potassium carbonate (17.2 grams, 0.125 mole) andN,N-dimethylformamide (150 mililiters) are added to a reactor andstirred under a nitrogen atmosphere with heating to reflux (154 deg.C.). After 6 hours, at the reflux, high pressure liquid chromatographicanalysis demonstrates that complete conversion or the4,4'-dihydroxy-alpha-methylstilbene to a single major product hasoccurred. At this time, the reaction slurry is cooled to roomtemperature (24 deg. C.), filtered, then rotary evaporated to provide asolid product. The solid is slurried into a minimum or toluene, stirred,then filtered. The product recovered from the filter is dried in avacuum oven at 80 deg. C. and one mm Hg to a constant weight of 14.0grams of Light yellow colored crystalline product. The melting point ofthe product measured in a glass capillary tube is 155-157 deg. C. andhas a turbid appearance. Continued heating to above 160 deg. C. providesa clear melt. Differential scanning calorimetry is completed usingportions (9.0 and 9.1 milligrams) of the product and a heating rate of10 deg. C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature from 30 deg. C. to 250 deg. C.A single sharp endotherm is obtained with a minimum at 161.9 deg. C. andan enthalpy of 77.2 joules per gram (average of two samples). Analysisof a portion of the product via microscopy under a crosspolarized lightsource is completed using a microscope equipped with a programmable hotstage using a heating rate of 10 deg. C. per minute and 70×magnification. The following results are obtained: at 30 deg. C., theproduct is a birefringent crystalline solid; at 152.5 deg. C. the firstfluidity is observed; at 157.5 deg. C., the product appears as crystalsdispersed in an isotropic fluid; isotropization is complete at 160 deg.C., with a trace amount of birefringence apparent in the fluid and aminor amount of birefringent specks also present therein. Upon coolingfrom 170 deg. C., crystallization occurs at 112.7 deg. C. Fouriertransform infrared spectrophotometric analysis of a potassium bromidepellet of the product reveals the presence of the expected assymetricnitro group stretching at 1510 cm⁻¹, the symmetric nitro groupstretching at 1344 cm⁻¹, aromatic C--O vibration at 1244 cm⁻¹ and C--Hout-of-plane deformation at 879 cm⁻¹ for the R₂ C═CHR group.

C. Synthesis and Characterization of4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene

4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene (11.7 grams, 0.05 nitroequivalent) from B above and ethyl acetate (200 milliliters) are addedto a 400 milliliters heavy walled glass bottle and then sparged withnitrogen. After removal of the air by nitrogen sparging, Raney nickelcatalyst (5.0 gram of a 50% wt. slurry in water at pH 10 washed oncewith deionized water) is added to the bottle which is then stoppered andmultiply purged with hydrogen to replace the nitrogen atmosphere. Thebottle is then placed on a shaking type agitator and pressurized to 50psig with hydrogen. Shaking of the pressurized bottle, at roomtemperature (24 deg. C.) commences until 28 minutes later, the hydrogenpressure reading indicates that 12.5 psig of hydrogen has been consumed.After an additional 7 minutes under hydrogen pressure, no furtherhydrogen uptake occurs and the reaction slurry is recovered and filteredto remove the Raney nickel, then rotary evaporated to provide a solidproduct (9.5 grams). The softening point of a portion of the productmeasured in a glass capillary tube is 135 deg. C. with melting observedat 148-150 deg. C. Differential scanning calorimetry is completed usingportions (9.8 and 9.5 milligrams) of the product and a heating rate of10 deg. C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30-250 deg. C. Apair of endotherms are obtained with minima at 138.9 deg. C. and 159.9deg. C. and enthalpies of 15.9 joules per gram and 86.3 joules per gram,respectively (average of two samples). Analysis of a portion of theproduct via microscopy under a crosspolarized light source is completedusing a microscope equipped with a programmable hot stage using aheating rate of 10 deg. C. per minute and 70× magnification. Thefollowing results are obtained: at 30 deg. C., the produce is abirefringent crystalline solid; at 139 deg. C., softening is observed;at 152 deg. C., the first fluidity is observed; between 152-157 deg. C.,the product appears as crystals dispersed in an isotropic fluid;isotropization is complete at 157 deg. C., with a minor amount ofbirefringent specks present in the fluid. Upon cooling from 165 deg. C.,crystallization occurs at 87 deg. C. Fourier transform infraredspectrophotometric analysis of a potassium bromide pellet of the productreveals the presence of the expected primary amine group N--H stretchingat 3396, 3336 and 3216 (shoulder) cm⁻¹ concurrent with the completedisappearance of the assymetric and symmetric nitro group stretching,C--H stretching absorbance of the aromatic rings and ═C--H at 3044 cm⁻¹,NH₂ deformation at 1629 cm⁻¹, absorbance in the C═C stretching region at1603 cm⁻¹, aromatic ring stretching absorbance at 1503 cm⁻¹, aromaticC--O vibration at 1238 cm⁻¹, (shoulder at 1278 cm⁻¹ due to aromatic C--Nstretch vibration), C--H out-of-plane deformation at 879 cm⁻¹ for the R₂C═CHR group and out-of-plane C--H bending vibration at 826 (846shoulder) cm⁻¹ indicative of paradisubstitution. Decoupled C¹³ nuclearmagnetic resonance spectroscopic analysis reveals a complete lack ofpeaks in the chemical shift range of 0 to 115 ppm (versustetramethylsilane), except a single peak at 17.1 ppm due to the alpha--CH₃ on the stilbene linkage, thus demonstrating the integrity of thestilbenic unsaturation. Titration of a portion of the product provides a99.35 --NH equivalent weight versus a theoretical 102.12 equivalentweight.

EXAMPLE 2 A. Synthesis of 4,4'-Diglycidyloxy-alpha-methylstilbene

4,4'-Dihydroxy-alpha-methylstilbene (452.5 grams, 4.0 hydroxylequivalents) prepared using the method of Example 1-A, epichlorohydrin(1850.6 grams, 20.0 moles), deionized water (160.9 grams, 8.0 percent byweight of the epichlorohydrin used) and isopropanol (996.5 grams, 35percent by weight of the epichlorohydrin used) are added to a reactorand heated to 50 deg. C. with stirring under a nitrogen atmosphere. Oncethe 50 deg. C. temperature is achieved, sodium hydroxide (144.0 grams,3.60 moles) dissolved in deionized water (576.0 grams) is added dropwiseto the reactor over a 45 minute period and so as to induce an exothermicincrease in temperature to 63 deg. C., with subsequent maintenance ofthe temperature at 55 deg. C. Ten minutes after completion of theaqueous sodium hydroxide addition, the stirring is stopped and theaqueous layer which separates from the reaction mixture is pipetted offand discarded. Stirring is resumed and after a total of 20 minutesfollowing the completion of the initial aqueous sodium hydroxideaddition, a second solution of aqueous sodium hydroxide (64.0 grams,1.60 mole) dissolved in deionized water (256.0 grams) is added to thereactor over a 20 minute period with maintenance of the 53 deg. C.reaction temperature. Fifteen minutes after completion of the aqueoussodium hydroxide, the recovered reaction mixture is added to a pair of 2liter separatory funnels and each portion washed with warm (60-70 deg.C.) deionized water (375 milliliters). The separated organic layers arewashed a second and third time (375 milliliters of warm deionized wateris used for each washing), recovered and then rotary evaporated undervacuum using final conditions of 150 deg. C. and one mm Hg for 2 hours.After removal from the rotary evaporator, the molten epoxy resin, isvacuum filtered through a heated (175 deg. C.) medium fritted glassfunnel, then poured into an aluminum foil tray to solidify. The4,4'-diglycidyloxy-alpha-methylstilbene is recovered (648.1 grams) as acrystalline white solid. Titration of portions of the diglycidyl etherproduct reveals an epoxide equivalent weight (EEW) of 178.56. Analysisof a portion of the diglycidyl ether product via microscopy undercrosspolarized light is completed at 70× magnification using amicroscope equipped with a programmable hot stage using a heating rateof 10 deg. C. per minute and a range of 30 to 150 deg. C., immediatelyfollowed by cooling. Isotropization is observed at 128-129 deg. C.,liquid crystallinity occurs at 95 deg. C. and crystallization occurs at66 deg. C. The diglycidyl ether gives monotropic liquid crystallinitywith a nematic liquid crystalline texture.

B. Preparation and Copolymerization of a Curable Blend of4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (0.1211 gram, 0.001219 --NH equivalents) of4,4'-bis-(4-aminophenoxy)-alpha-methylstilbene from Example 1-C and aportion (0.2177 gram, 0.001219 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from A above are dissolved inmethylene chloride (3 milliliters). The solution is devolatilized undera nitrogen sparge, then dried in a vacuum oven at 25 deg. C. and one mmHg to a constant weight. Differential scanning calorimetry is completedusing portions (11.9 and 10.4 milligrams) of the blend and a heatingrate of 10 deg. C. per minute under a stream of nitrogen flowing at 35cubic centimeters per minute and a temperature range from 30 to 250 deg.C. An endotherm is obtained with a minimum at 108.4 deg. C. and anenthalpy of 79.2 joules per gram. An exotherm is obtained with a maximumat 176.3 deg. C. and an enthalpy of 307.7 joules per gram (average oftwo samples). A second heating is completed using the aforementionedconditions with no residual cure energy and no glass transitiontemperature observed. Analysis of the pale yellow colored, transparentcured product recovered from the differential scanning calorimetryanalysis via microscopy under crosspolarized light is completed andreveals the presence of a nematic liquid crystalline texture. Analysisof a portion of the curable blend via microscopy under crosspolarizedlight is completed using a microscope equipped with a programmable hotstage using a heating rate of 10 deg. C. per minute and 70×magnification. The following results are obtained: at 30 deg. C., theblend is a birefringent crystalline solid; at 89 deg. C., softening isfirst observed; at 98 deg. C., fluidity is first observed; at 102 deg.C., the blend is an isotropic fluid containing birefringent crystals; at122 deg. C., isotropization is complete; at 155 deg. C., the fluidbecomes highly viscous; at 159 deg. C., numerous birefringent specksform; at 172 deg. C., thermosetting occurs with retention of thebirefringent specks. A second portion of the blend is analyzed using theaforementioned conditions with heating to 165 deg. C. and is found to behighly birefringent and stir opalescent when removed from the hot stageat this temperature and allowed to cool. A third portion of the blendbetween a glass slide and coverslip is placed on the stage which ispreheated to 165 deg. C. After 40 seconds a viscous isotropic fluidforms. The sample is removed from the heated stage at this time andsheared between the coverslip and slide while cooling, resulting inopalescence. Once cooled to room temperature (24 deg. C.), the solid isobserved by microscopy under crosspolarized light and found to possess amixture of textures, including smectic liquid crystalline texture.

EXAMPLE 3 Preparation of a Casting from a Curable Blend of4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (3.97 grams, 0.0399 --NH equivalents) of4,4'-bis(4-aminophenoxy)-alpha-methylstilbene from Example 1-C and aportion (7.13 grams, 0.0399 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A are dissolvedin methylene chloride (30 milliliters). The solution is devolatilizedunder a nitrogen sparge, then dried in a vacuum oven at 25 deg. C. andone mm Hg to a constant weight. A portion (0.85 gram) of the curableblend is placed in an aluminum dish then put into an oven preheated to140 deg. C. After one minute, a partial melt is achieved and is stirred.After a total of 2 minutes, a translucent viscous liquid is obtained.After a total of 5 minutes, the viscous translucent liquid resin istransferred to an oven preheated to 120 deg. C. After a total of 11minutes, the resin gels to an opaque solid. After a total of 3 hours at120 deg. C., the temperature in the oven is increased by 20 deg. C.every hour. After 180 deg. C. is achieved, the temperature in the ovenis increased to 200 deg. C. and maintained therein for the next fourhours. After cooling the oven, the recovered casting is opaque.Microscopy under crosspolarized light reveals the presence ofbirefringent domains and liquid crystal textures. Differential scanningcalorimetry is completed using portions (60 and 60 milligrams) of thecured casting and a heating rate of 10 deg. C. per minute under a streamof nitrogen flowing at 35 cubic centimeters per minute and a temperaturerange from 30 to 300 deg. C. No glass transition temperature or anyother events are observed (average of two samples).

EXAMPLE 4 Preparation of an Injection Molded Casting from a CurableBlend of 4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (6.5 grams) of the curable blend from Example 3 is placed intothe reservior of an injection molder proheated to 145 deg. C. Periodicstirring commences and after a total of 4 minutes in the reservoir, atranslucent melt is obtained. After an additional minute of heating inthe reservoir, the resin is injected through a 0.020 inch by 0.375 inch(0.5 by 9.5 mm) rectangular flow gate into a mold preheated to 80 deg.C. and having the following dimensions: 3.0 inches by 0.5 inch by 0,125inch (76.2 by 12.7 by 3.125 mm). At the time of injection molding, asample of the resin is removed from the reservoir and cooled to roomtemperature (23 deg. C.). A portion of this sample removed beforecooling is placed on a stage preheated to 145 deg. C. and examined bymicroscopy under crosspolarized light at 70× magnification. Thismicroscopic examination reveals the presence of a dispersed birefringentphase and phase segregated regions which have liquid crystal textures.After 15 seconds at 145 deg. C., cooling at a rate of 10 deg. C. perminute commences. At 132 deg. C., an increase in the birefringent phaseis observed. At 130 deg. C., the resin is opaque and barely mobile. Atthis time, shearing of the resin by moving the glass coverslip over theslide produces birefringent striations in the direction that the shearis applied. Portions (21.4 and 12.7 milligrams) of the sample removedfrom the reservoir at the time of injection molding are analyzed bydifferential scanning calorimetry using a heating rate of 10 deg. C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30 to 300 deg. C. An exotherm isobtained with a maximum at 139.9 deg. C. and an enthalpy of 168.4 joulesper gram. The mold is removed from the injection molder immediatelyafter completion of the resin injection then placed in an oven preheatedto 80 deg. C. After a total of 3 hours at 80 deg. C., the temperature inthe oven is increased by 20 deg. C. every hour. After 160 deg. C. isachieved, the temperature in the oven is increased to 180 deg. C. andmaintained therein for the next 4 hours. After cooling the oven, therecovered casting is opaque and contains birefringent domains whenviewed by microscopy under crosspolarized light at 70× magnification.Differential scanning calorimetry is completed using portions (60 and 60millgrams) of the cured casting and a heating rate of 10 deg. C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30 to 300 deg. C. No glasstransition temperature or any other events are observed (average of twosamples).

EXAMPLE 5 Preparation of a Casting from a Curable Blend of4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene and Diglycidyl Ether ofBisphenol A

A portion (2.382 grams, 0.0233 --NH equivalents) of4,4'-bis(4-aminophenoxy)-alpha-methylstilbene (102.1 --NH equivalentweight) prepared using the method of Example 1-C and a portion (4.046grams, 0.0233 epoxide equivalents) of diglycidyl ether of hisphenol A(173.39 epoxide equivalent weight) are mixed in an aluminum pan to ahomogeneous paste. Analysis of a portion of the blend via microscopyunder a crosspolarized light source is completed using a microscopeequipped with a programmable hot stage using a heating rate of 10 deg.C. per minute an 70× magnification. The following results are obtained:at 30 deg. C., the product is a slurry of birefringent crystallinediamine dispersed in the epoxy resin, at 97 deg. C., the diaminecrystals are beginning to dissolve; at 112 deg. C., in excess of 95% ofthe diamine crystals are dissolved with mixing; at 117-124 deg. C., allremaining diamine crystals have dissolved. Once 130 deg. C. is reached,cooling at a rate of 10 deg. C. per minute commences until 45 deg. C. isreached. At this time, a dispersed birefringent phase is observed in thetranslucent viscous resin. Portions (15.9 and 23.3 milligrams) of thecurable blend are analyzed by differential scanning calorimetry using aheating rate of 10 deg. C. per minute under a stream of nitrogen flowingat 35 cubic centimeters per minute and a temperature range from 30 to300 deg. C. An exotherm is obtained with a maximum at 179.1 deg. C. andan enthalpy of 311.9 joules per gram (average of two samples). Theremaining curable blend is placed in an aluminum dish then put into anoven preheated to 145 deg. C. After a total of 4 minutes, a translucentviscous liquid is obtained and the temperature in the oven is reduced to120 deg. C. After fours at 120 deg. C., the temperature in the oven isincreased by 20 deg. C. every hour. After 180 deg. C. is achieved, thetemperature in the oven is increased to 200 deg. C. and maintainedtherein for the next 4 hours. After cooling the oven, the recoveredcasting is translucent and slightly hazy. Microscopy undercrosspolarized light reveals the presence of birefringent liquid crystaltextures. Differential scanning calorimetry is completed using portions(40 and 40 milligrams) of the cured casting and a heating rate of 10deg. C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30 to 300 deg. C. Aglass transition temperature of 179.4 deg. C. is detected (average oftwo samples).

EXAMPLE 6 Dynamic Mechanical, Analysis Of an Injection Molded Castingfrom a Curable Blend of 4,4'-bis(4-Aminophenoxy)-alpha-methylstilbeneand 4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (31.33 by 3.84 by 3.09 mm) of the injection molded castingfrom Example 4 is subjected to dynamic mechanical analysis in theresonant mode using standard methods (ASTM D 4065-82). A 5 deg. C. perminute rate of heatup is employed with a temperature range of 30 to 250deg. C. Storage modulus (E') values thus determined are as follows forselected temperatures. The maximum temperature observed for the tandelta transition is 168.6 deg. C.

    ______________________________________                                        Temperature (deg. C.)                                                                         Storage Modulus (GPa)                                         ______________________________________                                         35             2.814                                                          93             1.744                                                         121             1.388                                                         149             0.9658                                                        177             0.4611                                                        204             0.3016                                                        232             0.2498                                                        ______________________________________                                    

EXAMPLE 7 A. Synthesis of 4,4'-bis(2-Nitrophenoxy)-alpha-methylstilbene

4,4'-Dihydroxy-alpha-methylstilbene (22.6 grams, 0.20 hydroxylequivalent) from Example 1-B, o-chloronitrobenzene (39.4 grams, 0.25mole), -325 mesh anhydrous potassium carbonate (34.5 grams, 0.25 mole)and N,N-dimethylformamide (200 mililiters) are added to a reactor andstirred under a nitrogen atmosphere with heating to 130 deg. C. After 9hours at the 130 deg. C. temperature, high pressure liquidchromatographic analysis demonstrates that complete conversion of the4,4'-dihydroxy-alpha-methylstilbene to a single major product hasoccurred. At this time, the reaction slurry is cooled to roomtemperature (24 deg. C.), filtered, then rotary evaporated to a constantweight of 53.6 grams of reddish brown colored liquid product.

B. Synthesis and Characterization of4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene

4,4'-bis(2-Nitrophenoxy)-alpha-methylstilbene (48.6 grams, 0.2075 nitroequivalent) from B above and ethyl acetate (500 milliliters) are addedto a one liter stainless steel pressure bottle and then sparged withnitrogen. After removal of the air by nitrogen sparging, Raney nickelcatalyst (10.0 gram of a 50% wt. slurry in water at pH 10 washed twicewith with 25 milliliter portions of deionized water then twice with 25milliliter portions of isopropanol) is added to the bottle which is thenstoppered and multiply purged with hydrogen to replace the nitrogenatmosphere. The bottle is then placed on a shaking type agitator andpresurrized to 50 psig with hydrogen. Shaking of the pressurized bottleat room temperature (24 deg. C.) commences until 106 minutes later, thehydrogen pressure reading indicates that 44 psig of hydrogen has beenconsumed. After an additional 15 minutes under hydrogen pressure, nofurther hydrogen uptake occurs and the reaction slurry is recovered andfiltered to remove the Raney nickel, then rotary evaporated to provide atotal volume of 100 milliliters. n-Hexane (100 milliliters) is added tothe concentrated solution followed by cooling in an ice bath. The solidprecipitate is recovered by filtration then washed with a minimum of a1:1 volume mixture of ethyl acetate:n-hexane. The product recovered fromthe filter is dried in a vacuum oven at 80 deg. C. and one mm Hg to aconstant weight of 28.7 grams of light amber colored product. Themelting point of a portion of the product measured in a glass capillarytube is observed at 104-106 deg. C. Differential scanning calorimetry iscompleted using portions (9.5 and 8.1 milligrams) of the product and aheating rate of 10 deg. C. per minute under a stream of nitrogen flowingat 35 cubic centimeters per minute and a temperature range from 30-160deg. C. An endotherm is obtained with a minimum at 109.7 deg. C. and anenthalpy of 74.0 joules per gram (average of two samples). Analysis of aportion of the product via microscopy under a crosspolarized lightsource is completed using a microscope equipped with a programmable hotstage using a heating rate of 10 deg. C. per minute and 70×magnification. The following results are obtained: at 30 deg. C., theproduct is a birefringent crystalline solid; at 99 deg. C., softening isobserved; at 100 deg. C., the product appears as crystals dispersed inan isotropic fluid; isotropization is complete at 107.4 deg. C. Uponcooling from 110 deg. C., initial crystallization is observed at 61 deg.C. Fourier transform infrared spectrophotometric analysis of a neat filmof the product on a potassium chloride plate reveals the presence of theexpected primary amine group N-H stretching at 3469, 3376 and 3210 cm⁻¹concurrent with the complete disappearance of the assymetric andsymmetric nitro group stretching, C--H stretching absorbance of thearomatic rings and═C--H at 3037 (3044 shoulder) cm⁻¹, NH₂ deformation at1616 cm⁻¹, absorbance in the C═C stretching region at 1603 cm⁻¹,aromatic ring stretching absorbance at 1503 cm⁻¹, aromatic C--Ovibration at 1224 cm⁻¹, (shoulder at 1271 cm⁻¹ due to aromatic C--Nstretch vibration), C--H out-of-plane deformation at 879 cm⁻¹ for the R₂C═CHR group, out-of-plane C--H bending vibration at 832 (846 slightshoulder) cm⁻¹ indicative of para-disubstitution and out-of-plane C--Hbending vibration at 746 cm⁻¹ indicative of ortho-disubstitution.Decoupled C¹³ nuclear magnetic resonance spectroscopic analysis revealsa complete lack of peaks in the chemical shift range of 0 to 115 ppm(versus tetramethylsilane), except a single peak at 17.5 ppm due to thealpha --CH₃ on the stilbene linkage, thus demonstrating the integrity ofthe stilbenic unsaturation. Proton magnetic resonance spectroscopicanalysis (250 MHz) reveals a singlet at 2.25 ppm for the --CH₃, a broadsinglet at 3.80 ppm and a multiplet between 6.70-7.47 ppm for thearomatic ring hydrogens and the stilbenic ═C--H. Titration of a portionof the product provides a 103.357 --NH equivalent weight versus atheoretical 102.12 equivalent weight.

In a repeat of the aforementioned synthesis,4,4'-bis(2-aminophenoxy)-alpha-methylstilbene (53.6 grams) ishydrogenated, the reaction slurry is recovered and filtered to removethe Raney nickel, then rotary evaporated at 120 deg. C. and one mm Hguntil residual o-chloroaniline is removed. The light amber coloredproduct thus recovered (40.4 grams) solidifies on standing. Titration ofa portion of the product provides a 103.189 --NH equivalent weightversus a theoretical 102.12 equivalent weight.

EXAMPLE 8 Preparation and Copolymerization of a Curable Blend of4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (6.17 grams, 0.0598 --NH equivalents) of4,4'-bis(2-aminophenoxy)-alpha-methylstilbene from Example 7-B and aportion (10.68 grams, 0.0598 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A are dissolvedin methylene chloride (30 milliliters). The solution is devolatilizedunder a nitrogen sparge, then dried in a vacuum oven at 25 deg. C. andone mm Hg to a constant weight. Differential scanning calorimetry iscompleted using portions (12.9 and 19.5 milligrams) of the blend and aheating rate of 10 deg. C. per minute under a stream of nitrogen flowingat 35 cubic centimeters per minute and a temperature range from 30 to300 deg. C. An endotherm is obtained with a minimum at 117.4 deg. C. andan enthalpy of 27.3 joules per gram. An exotherm is obtained with amaximum at 207.6 deg. C. and an enthalpy of 237.6 joules per gram(average of two samples). A second heating is completed using theaforementioned conditions with a glass transition temperature of 146.5deg. C. and no residual cure energy observed. Analysis of thetranslucent cured product recovered from the differential scanningcalorimetry analysis via microscopy under crosspolarized light iscompleted using a microscope equipped with a programmable hot stageusing a heating rate of 10 deg. C. per minute and 70× magnification. Ahigh level of birefringence is observed. Analysis of a portion of thecurable blend via microscopy under crosspolarized light is completedusing a microscope equipped with a programmable hot stage using aheating rate of 10 deg. C. per minute and 70× magnification. Thefollowing results are obtained: at 30 deg. C., the blend is abirefringent crystalline solid; at 70 deg. C., partial melting isobserved with dispersed crystals present; at 109 deg. C., partialclearing of the crystals is observed; at 124 deg. C., isotropization isComplete. Heating is continued to 130 deg. C. and after 32 minutesthermosetting occurs to a non-birefringent transparent solid whichexhibits birefringence when scratched with a steel needle. A secondportion of the blend between a glass slide and coverslip is placed onthe stage which is preheated to 130 deg. C. After 45 seconds anisotropic fluid forms and cooling at 10 deg. C. per minute commences,with the following results: at 82 deg. C., a minor amount ofbirefringent domains are observed; at 71 deg. C., a minor amount ofliquid crystal texture is observed; at 60 deg. C., the resin istranslucent; at 45 deg. C. the translucent resin is barely mobile. Atthis time, the sample is removed from the heated stage at this time andsheared between the coverslip and slide while cooling, resulting in nochange in the morphology. Once cooled to room temperature (24 deg. C.),the tacky semi-solid is observed by microscopy under crosspolarizedlight and found be non-birefringent except for dispersed crystalspresent.

EXAMPLE 9 Preparation of a Casting from a Curable Blend of4,4'bis(2-Aminophenoxy)-alpha-methylstibene and4,4'-Diglycidyloxy-alpha-methylstilbene

A portion (3.51 grams) of the curable blend of4,4'-bis(4-aminophenoxy)-alpha-methylstilbene and4,4'-diglycidyloxy-alpha-methylstilbene from Example 8 is placed in analuminum dish then put into an oven preheated to 130 deg. C. After twominutes, a partial melt is achieved and is stirred. After a total of 10minutes, a translucent viscous liquid is obtained. After a total of 15minutes, the translucent viscous liquid is sampled for differentialscanning calorimetry and microscopy. Once cooled to room temperature (24deg. C.), microscopy under crosspolarized light reveals the presence ofsmall birefringent domains and liquid crystal textures. Differentialscanning calorimetry is completed using portions (22.3 and 20.2milligrams) of the sample and a heating rate of 10 dec. C. per minuteunder a stream of nitrogen flowing at 35 cubic centimeters per minuteand a temperature range from 30 to 300 deg. C. An endotherm is obtainedwith a maximum at 201.1 deg. C. and an enthalpy of 206.4 joules per gram(average of two samples). A second heating is completed using theaforementioned conditions with a glass transition temperature of 150.9deg. C. and no residual cure energy observed. After 35 minutes, theresin is near the gel point such that fibers can be drawn therefrom witha cold spatula. Once cooled to room temperature (24 deg. C.), microscopyunder crosspolarized light reveals a high level of birefringence in thefibers. A sample of the resin taken at this time and cooled to roomtemperature (24 deg. C.) is translucent and somewhat cloudy inappearance. Microscopy under crosspolarized light reveals the presenceof dispersed birefringent domains and liquid crystal textures. A secondportion of the sample of the resin taken at this time is placed betweena glass slide and coverslip then placed on the stage of a microscopewhich has been preheated to 130 deg. C. Cooling at 10 deg. C. per minutecommences until 80 deg. C. is reached, then the sample is removed fromthe heated stage and sheared between the coverslip and slide. Thegelatinous semi-solid resin exhibits a high level of birefringence as aresult of the shearing. Upon cooling to room temperature (24 deg. C.),the resin is a translucent solid which retains the high level ofbirefringence. After 45 minutes, the resin is a rubbery gel with atranslucent, cloudy appearance. After a total of 3 hours at the 130 deg.C. temperature, the temperature is increased 20 deg. C. every hour until200 deg. C. is achieved. The 200 deg. C. temperature is held for 4 hoursafter which time, the oven is allowed to gradually cool to roomtemperature (24 deg. C.) and the casting recovered and examined bymicroscopy under crosspolarized light. A high level of birefringence isobserved with a minor amount of a dispersed second phase. Differentialscanning calorimetry is completed using portions (60.0 and 60.0milligrams) of the casting and a heating rate of 10 deg. C per minuteunder a stream of nitrogen flowing at 35 cubic centimeters per minuteand a temperature range from 30 to 300 deg. C. A glass transitiontemperature of 159.3 deg. C. and no residual cure energy are observed(average of two samples).

EXAMPLE 10 Preparation of an Injection Molded Casting from a CurableBlend of 4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglylidyloxy-alpha-methylstilbene

A portion (7.07 grams) of the curable blend from Example 8 is placedinto an oven preheated to 130 deg. C. and stirred periodically. After 12minutes in the oven, melting has occurred and at this time, the resin ispoured into the reservoir of an injection molder preheated to 130 deg.C. After a total of 7 minutes in the reservoir, fibers can be drawn fromthe molten resin with a cold spatula. After an additional four minutesof heating in the reservoir, heating of the reservoir ceases. After anadditional minute, when the reservoir is at 128 deg. C. and the resin isnear its gel point, the resin is injected through a 0.020 inch by 0.375inch (0.5 by 9.5 mm) rectangular flow gate into a mold preheated to 80deg. C. and having the following dimensions: 3.0 inches by 0.5 inch by0.125 inch (76.2 by 12.7 by 3.125 mm). At the time of injection molding,a sample of the resin is removed from the reservoir and cooled to roomtemperature (24 deg. C.). A portion of this sample removed beforecooling is placed on a stage preheated to 130 deg. C. and examined bymicroscopy under crosspolarized light at 70× magnification. Thismicroscopic examination reveals the resin to be a viscous translucentnon-birefringent liquid. After 15 seconds at 130 deg. C., cooling at arate of 10 deg. C. per minute commences. At 100 deg. C., a low level ofbirefringence is observed. At this time, shearing of the resin by movingthe glass coverslip over the slide produces no change in the morphologyof the gelatinous mobile resin. At 80 deg. C., shear is again appliedand produces a high level of birefringence in the barely mobile resin.This same morphology is maintained upon cooling to room temperature (24deg. C.). Portions (14.6 and 21.3 milligrams) of the sample removed fromthe reservoir at the time of injection molding are analyzed bydifferential scanning calorimetry using a heating rate of 10 deg. C. perminute under a stream of nitrogen flowing at 35 cubic centimeters perminute and a temperature range from 30 to 300 deg. C. An exotherm isobtained with a maximum at 200.7 deg. C. and an enthalpy of 143.1 joulesper gram (average of two samples). The mold is removed from theinjection molder two hours after completion of the resin injection thenplaced in an oven preheated to 110 deg. C. After one hour at 110 deg.C., the temperature in the oven is increased by 10 deg. C. every hour.After 140 deg. C. is achieved, the temperature in the oven is increasedby 20 deg. C. every hour. After 200 deg. C. is achieved, the temperaturein the oven is maintained therein for the next 2 hours. Alter coolingthe oven, the recovered casting is translucent and possesses a highlevel of birefringence when viewed by microscopy under crosspolarizedlight at 70× magnification. The flashing around the edges of the castingexhibits a flow oriented striated birefringent texture. Differentialscanning calorimetry is completed using portions (60 and 60 millgrams)of the cured casting and a heating rate of 10 deg. C. per minute under astream of nitrogen flowing at 35 cubic centimeters per minute and atemperature range from 30 to 300 deg. C. A glass transition temperatureof 155.8 deg. C. and no residual cure energy are observed (average oftwo samples).

EXAMPLE 11 Preparation of a Casting from4,4'-Diglycidyloxy-alpha-methylstilbene Cured with4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene and Determination ofFlexural Properties

A portion (14.49 grams, 0.1402 --NH equivalent) of4,4'-bis(4-aminophenoxy)-alpha-methylstilbene prepared using the methodof Example 7-B (second synthesis) (103.357 --NH equivalent weight) and aportion (25.03 grams, 0.1402 epoxide equivalent) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A are placed inovens preheated to 130 and 150 deg. C., respectively. After melts areachieved, the two components are combined and stirred for the next 4.5minutes, followed by degassing for 1.5 minutes in a vacuum bell jar.After degassing, the resin is poured into a glass mold (5 inch by 4 inchby 0.125 inch) preheated to 130 deg. C. After 4 hours at 130 deg. C.,the temperature of the oven is increased to 140 deg. C. After one hourat 140 deg. C., the temperature in the oven is increased by 20 deg. C.every hour. After 200 deg. C. is achieved, the temperature in the ovenis maintained therein for the next 2 hours. After cooling the oven, therecovered casting is translucent and possesses a high level ofbirefringence when viewed by microscopy under crosspolarized light at70× magnification. Differential scanning calorimetry is completed usingportions (80 and 40 milligrams) of the cured casting and a heating rateof 10 deg. C. per minute under a stream of nitrogen flowing at 35 cubiccentimeters per minute and a temperature range from 30 to 300 deg. C. Aglass transition temperature of 165.5 deg. C. and no residual cureenergy are observed (average of two samples). A series of five testpieces are cut from the casting for testing of flexural properties usingstandard methods (ASTM D 790-86). The average flexural strength thusobtained is 14,982 psi and the average flexural modulus is 443,100 psi.All of the test pieces yielded without breaking (percent strain >15).

EXAMPLE 12 Dynamic Mechanical Analysis of a Casting from4,4'-Diglycidyloxy-alpha-methylstilbene Cured with4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene

A portion (31.73 by 6.09 by 3.19 mm) of the casting from Example 11 issubjected to dynamic mechanical analysis in the resonant mode usingstandard methods (ASTM D 4065-82). A 5 deg. C. per minute rate of heatupis employed with a temperature range of 30 to 250 deg. C. Storagemodulus (E') values thus determined are as follows for selectedtemperatures. The maximum temperature observed for the tan deltatransition is 196.3 deg. C.

    ______________________________________                                        Temperature (deg. C.)                                                                         Storage Modulus (GPa)                                         ______________________________________                                         30             2.933                                                          93             2.151                                                         121             1.735                                                         149             1.272                                                         177             0.5183                                                        204             0.0751                                                        232             0.0279                                                        ______________________________________                                    

EXAMPLE 13 Single Edge Notch Three Point Bend Testing of a Casting from4,4'-Diglycidyloxy-alpha-methylstilbene Cured with4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene

A portion (50.02 grams, 0.4814 --NH equivalent) of4,4'-bis(2-aminophenoxy)-alpha-methylstilbene prepared using the methodof Example 7-B (second synthesis) (103.916 --NH equivalent weight) and aportion (85.95 grams, 0.4814 epoxide equivalent) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A are placed inovens preheated to 130 and 150 deg. C., respectively. After melts areachieved, the two components are combined are combined and stirred forthe next 2.5 minutes, followed by degassing for 30 seconds in a vacuumbell jar. After degassing, the resin is poured into a glass mold (6 inchby 5 inch by 0.250 inch) preheated to 130 deg. C. After 4 hours at 130deg. C., the temperature of the oven is increased to 140 deg. C. Afterone hour at 140 deg. C., the temperature in the oven is increased 160deg. C. After one hour at 160 deg. C., the temperature in the oven isincreased 180 deg. C. After one hour at 180 deg. C., the temperature inthe oven is increased 200 deg. C. After 200 deg. C. is achieved, thetemperature in the oven is maintained therein for the next 2 hours.After cooling the oven, the recovered casting is translucent andpossesses a high level of birefringence when viewed by microscopy undercrosspolarized light at 70× magnification. Differential scanningcalorimetry is completed using portions (80 and 80 millgrams) of thecured casting and a heating rate of 10 deg. C. per minute under a streamof nitrogen flowing at 35 cubic centimeters per minute and a temperaturerange from 30 to 300 deg. C. A glass transition temperature of 153.5deg. C. and no residual cure energy are observed (average of twosamples). A series of eleven test pieces are cut from the casting forsingle edge notch three point bend testing using standard methods (ASTME 399-83). The average G_(1c) thus obtained is 702 joules/m² and theaverage K_(1c) is 1.57 MPa·m⁰.5.

EXAMPLE 14 Preparation of a Casting from4,4'-Diglycidyloxy-alpha-methylstilbene Cured with4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene and Determination ofTensile Properties

A portion (35.92 grams, 0..3389 --NH equivalent) of4,4'-bis(4-aminophenoxy)-alpha-methylstilbene prepared using the methodof Example 7-B (second synthesis) (105.98 --NH equivalent weight) and aportion (60.25 grams, 0.3389 epoxide equivalent) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A are placed inovens preheated to 130 and 150 deg. C., respectively. After melts areachieved, the two components are combined and stirred for the next 3minutes, followed by degassing for 30 seconds in a vacuum bell jar.After degassing, the resin is poured into a glass mold (7.5 inch by 6inch by 0.125 inch) preheated to 130 deg. C. After 4 hours at 130 deg.C., the temperature of the oven is increased to 140 deg. C. After onehour at 140 deg. C., the temperature in the oven is increased to 160deg. C. After one hour at 160 deg. C., the temperature in the oven isincreased to 180 deg. C. After one hour at 180 deg. C., the temperaturein the oven is increased to 200 deg. C. After 200 deg. C. is achieved,the temperature in the oven is maintained therein for the next 2 hours.After cooling the oven, the recovered casting is translucent andpossesses a high level of birefringence when viewed by microscopy undercrosspolarized light at 70× magnification. Differential scanningcalorimetry is completed using portions (40 and 40 millgrams) of thecured casting and a heating rate of 10 deg. C. per minute under a streamof nitrogen flowing at 35 cubic centimeters per minute and a temperaturerange from 30 to 300 deg. C. A glass transition temperature of 154.8deg. C. and no residual cure energy are observed (average of twosamples). A series of six Type I test pieces are cut from the castingfor testing of tensile properties using standard methods (ASTM D 638-89)(strain rate=0.2 inch/minute). The average tensile strength thusobtained is ]1,400 psi (+/-89 psi), the average tensile modulus is429,000 psi (+/-23,000 psi) and the elongation to break is 11.2%(+/-0.6%).

EXAMPLE 15 Preparation and Copolymerization of a Curable Blend of4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene,4,4'-bis(4-Aminophenoxyl)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene at a 1:1 Weight Ratio

A portion (3.4422 grams, 0.01928 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A is placed in anoven preheated to 150 deg. C. After a melt is achieved,4,4'-bis(2-aminophenoxy)-alpha-methylstilbene (1.0000 grams, 0.00948--NH equivalent) and 4,4'-bis(4-aminophenoxy)-alpha-methylstilbene(1.0000 grams, 0.00979 --NH equivalent) are combined with the moltenepoxy resin and stirred every 2-3 minutes, while maintained in a 130deg. C. oven. After 6 minutes, the resin is a homogeneous solution.After an additional 4 minutes, the blend is added to an aluminum dishheld in the 130 deg. C. oven. One minute later, a sample of the blend isremoved for analysis. Analysis via microscopy under crosspolarized lightis completed using a microscope equipped with a programmable hot stageusing a heating (cooling) rate of 10 deg. C. per minute and 70×magnification. The following results are obtained: at 130 deg. C., theblend is a translucent melt containing a trace of crystals; at 72 deg.C., additional crystals form, but the overall amount is still minor; at54 deg. C. the amount of crystals continues to increase; at 48 deg. C.,a liquid crystal phase starts to form; at 46 deg. C., shear is appliedby moving the coverslip over the slide, resulting in opalescence and theformation of small needlelike domains which are oriented perpendicularto the direction that the shear is applied. Nine minutes after theinitial sample of the blend is taken for analysis, a second sample istaken and analyzed via microscopy under crosspolarized light using theaforementioned conditions. The following results are obtained: at 130deg. C., the blend is a viscous, translucent melt free of crystals; at80.7 deg. C., a liquid crystal phase starts to form; at 75 deg. C.,shear is applied by moving the coverslip over the slide, resulting insmectic textures being observed 5 minutes after the sample is shearedand held at the 75 deg. C. temperature. Orientation of the fiberlikedomains is observed perpendicular to the direction that the shear isapplied. Fifteen minutes after the initial sample of the blend is takenfor analysis, a third sample (opaque, tack free solid when cooled toroom temperature) is taken and analyzed via microscopy undercrosspolarized light using the aforementioned conditions. The followingresults are obtained: at 130 deg. C., the blend is a viscous,translucent melt free of crystals; at 110 deg. C., a liquid crystalphase forms; at 100 deg. C., shear is applied by moving the coverslipover the slide, resulting in orientation of the liquid crystallinebirefringent striations in the direction (parallel) that the shear isapplied. This same morphology is observed 5 minutes after the sample issheared and held at the 100 deg. C. temperature. Twenty minutes afterthe initial sample of the blend is taken for analysis, the blend is atranslucent gel which becomes an opaque solid at room temperature withliquid crystal textures observed via microscopy under crosspolarizedlight.

EXAMPLE 16 Preparation and Copolymerization of a Curable Blend of4,4'-bis(2-Aminophenoxy)-alpha-methylstilbene,4,4'-bis(4-Aminophenoxy)-alpha-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene at a 2:1 Weight Ratio

A portion (3.8517 grams, 0.02157 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A is placed in anoven preheated to 150 deg. C. After a melt is achieved,4,4'-bis(2-aminophenoxy)-alpha-methylstilbene (1,500 grams, 0.01422 --NHequivalent) and 4,4,-bis(4-aminophenoxy)-alpha-methylstilbene (0.7500grams, 0.00735 --NH equivalent) are combined with the molten epoxy resinand stirred every 2-3 minutes, while maintained in a 130 deg. C. oven.After 7 minutes, the resin is a homogeneous solution. After anadditional 3 minutes, the blend is added to an aluminum dish held in the130 deg. C. oven. One minute later, a sample of the blend is removed foranalysis. Analysis via microscopy under crosspolarized light iscompleted using a microscope equipped with a programmable hot stageusing a heating (cooling) rate of 10 deg. C. per minute and 70×magnification. The following results are obtained: at 130 deg. C., theblend is a translucent melt containing a trace of crystals; at 42 deg.C., additional crystals form, but the overall amount is still minor; at37 deg. C., a liquid crystal phase starts to form; at 35 deg. C., shearis applied by moving the coverslip over the slide, resulting in theformation of liquid crystalline birefringent striations oriented in thedirection (parallel) that the shear is applied. Nine minutes after theinitial sample of the blend is taken for analysis, a second sample istaken and analyzed via microscopy under crosspolarized light using theaforementioned conditions. The following results are obtained: at 130deg. C., the blend is a viscous, translucent melt containing a trace ofcrystals; at 60 deg. C., a liquid crystal phase starts to form; at 55deg. C., shear is applied by moving the coverslip over the slide,resulting in the formation of liquid crystalline birefringent striationsoriented in the direction (parallel) that the shear is applied beingobserved and birefringent needlelike domains 5 minutes after the sampleis sheared and held at the 55 deg. C. temperature. Orientation of theseneedlelike domains is observed perpendicular to the direction that theshear is applied. Fourteen minutes after the initial sample of the blendis taken for analysis, a third sample (opaque, rubbery solid when cooledto room temperature) is taken and analyzed via microscopy undercrosspolarized light using the aforementioned conditions. The followingresults are obtained: at 130 deg. C., the blend is a viscous,translucent melt free of crystals; at 75 deg. C., a liquid crystal phaseforms; at 70 deg. C., shear is applied by moving the coverslip over theslide, resulting in the formation of liquid crystalline birefringentstriations oriented in the direction (parallel) that the shear isapplied being observed and birefringent needlelike domains 5 minutesafter the sample is sheared and held at the 70 deg. C. temperature.Orientation of these needlelike domains is observed perpendicular to thedirection that the shear is applied, but is not as pronounced as thatobserved for the previous sample. Nineteen minutes after the initialsample of the blend is taken for analysis, a fourth sample (partiallyopaque solid when cooled to room temperature) is taken and analyzed viamicroscopy under crosspolarized light using the aforementionedconditions. The following results are obtained: at 130 deg. C., theblend is a viscous, translucent melt free of crystals; at 86 deg. C., aliquid crystal phase forms; at 80 deg. C., shear is applied to thebarely mobile blend by moving the coverslip over the slide, resulting inthe formation of liquid crystalline birefringent striations oriented inthe direction (parallel) that the shear is applied being observed. Fiveminutes after the sample is sheared and held at the 80 deg. C.temperature, liquid crystalline birefringent striations oriented in thedirection (parallel) that the shear is applied are still observed.Twenty nine minutes after the initial sample of the blend is taken foranalysis, the blend is a translucent rubbery gel which becomes apartially opaque solid at room temperature with birefringence but nodomain structures observed via microscopy under crosspolarized light.

EXAMPLE 17 Injection Molding of a Curable Blend of4,4'-bis(2-Aminphenoxy)-alpha-methylstilbene,4,4'-bis(4-Aminophenoxy)-alpha-methyl-methylstilbene and4,4'-Diglycidyloxy-alpha-methylstilbene at a 1:1Weight Ratio andDetermination of the Flexural Properties of the Injection Molded Casting

A portion (5.1633 grams, 0.02892 epoxide equivalents) of4,4'-diglycidyloxy-alpha-methylstilbene from Example 2-A is placed in anoven preheated to 150 deg. C. After a melt is achieved,4,4'-bis(2-aminophenoxy)-alpha-methylstilbene (1.5000 grams, 0.01423--NH equivalent) and 4,4'-bis(4-aminophenoxy)-alpha-methylstilbene(1.5000 grams, 0.01469 --NH equivalent) are combined with the moltenepoxy resin and stirred every 2-3 minutes, while maintained in a 130deg. C. oven. After 7.5 minutes, the resin solution is degassed under avacuum for 30 seconds. After an additional 75 seconds, the resin ispoured into the reservoir of an injection molder preheated to 120 deg.C. After a total of 12 minutes in the reservoir, the molten resin isviscous and translucent and heating to the reservoir ceases. After anadditional 4.5 minutes, the reservoir is at 100 deg. C., the resin isopaque and is injected through a 0.020 inch by 0.375 inch (0.5 by 9.5mm) rectangular flow gate into a mold preheated to 60 deg. C. and havingthe following dimensions: 3.0 inches by 0.5 inch by 0.125 inch (76.2 by12.7 by 3.125 mm). At the time of injection molding, a sample of theresin is removed from the reservoir and cooled to room temperature (24deg. C.). A portion of this sample removed before cooling is placed on astage preheated to 120 deg. C. and examined by microscopy undercrosspolarized light at 70× magnification. This microscopic examinationreveals the resin to be a viscous translucent liquid with a trace ofbirefringent phase present having a batonnet appearance. After 15seconds at 120 deg. C., cooling at a rate of 10 deg. C. per minutecommences. At 106 deg. C., the amount of birefringent domains increase.At 100 deg. C., shearing of the resin by moving the glass coverslip overthe slide produces birefringent striations in the direction that theshear is applied. At 90 deg. C., shear is again applied and producessome morphology with orientation perpendicular to the direction that theshear is aplied. This combined morphology of birefringent striationsboth parallel and perpendicular to the direction that the shear isapplied is maintained at 60 deg. C. at which point the resin solidifies.A second portion of this sample is placed on a stage and examined bymicroscopy under crosspolarized light at 70× magnification while heatingat 10 deg. C. per minute. At 30 deg. C., the resin is an opaque solid.At 112 deg. C., dispersed birefringent domains are observed. At 132 deg.C., some clearing of the birefringent phase is observed. At 180 deg. C.,the opaque resin containing birefringent domains thermosets. This samemorphology is maintained upon cooling to room temperature (24 deg. C.).Portions (19.1 and 20.1 milligrams) of the sample removed from thereservoir at the time of injection molding are analyzed by differentialscanning calorimetry using a heating rate of 10 deg. C. per minute undera stream of nitrogen flowing at 35 cubic centimeters per minute and atemperature range from 30 to 300 deg. C. An exotherm is obtained with amaximum at 168.7 deg. C. and an enthalpy of 185.4 joules per gram(average of two samples). The mold is removed from the injection molderimmediately after completion of the resin injection then placed in anoven preheated to 60 deg. C. After one hour at 60 deg. C., thetemperature in the oven is increased by 10 deg. C. every hour until atemperature of 120 deg. C. is achieved. After one hour at 120 deg. C.,the temperature in the oven is increased by 20 deg. C. every hour until180 deg. C. is achieved. After 180 deg. C. is achieved, the temperaturein the oven is maintained therein for the next 4 hours. After coolingthe oven, the recovered casting is opaque with flow patterns on itssurface and possesses birefringent domains when viewed by microscopyunder crosspolarized light at 70× magnification. The flashing around theedges of the casting exhibits birefringent liquid crystal domainsoriented perpendicular to the shear direction. Differential scanningcalorimetry is completed using portions (60 and 60 millgrams) of thecured casting and a heating rate of 10 deg. C. per minute under a streamof nitrogen flowing at 35 cubic centimeters per minute and a temperaturerange from 30 to 300 deg. C. A glass transition temperature of 157.7deg. C. and no residual cure energy are observed (average of twosamples). The casting is tested for flexural properties using standardmethods (ASTM D 790-86). The average flexural strength thus obtained is17,266 psi and the average flexural modulus is 554,600 psi.

What is claimed is:
 1. A bis(aminophenoxy)-alpha-substituted stilbenerepresented by the following Formula I ##STR9## wherein each R isindependently hydrogen or a hydrocarbyl or hydrocarbyloxy group havingfrom one to about 10 carbon atoms, a halogen atom, a nitro group, anitrile group or a --CO--R² group; each R¹ is independently hydrogen ora hydrocarbyl group having from one to about 10 carbon atoms; X is a##STR10## group each R² is independently hydrogen or a hydrocarbyl grouphaving from one to abut 10 carbon atoms; R³ is a hydrocarbyl grouphaving from one to about 10 carbon atoms and may be chlorine or anitrile group when n has a value of zero; and n has a value of zero orone.
 2. A bis(aminophenoxy)-alpha-substituted stilbene of claim 1wherein when R is a hydrocarbyl or hydrocarbyloxy group, it has from oneto about 4 carbon atoms and when it is a halogen atom, it is chlorine,bromine or fluorine; when R¹ is a hydrocarbyl group, it has from one toabout 6 carbon atoms; when R² is a hydrocarbyl group, it has from one toabut 2 carbon atoms; and when R³ is a hydrocarbyl group, it has from oneto about 2 carbon atoms.
 3. A bis(aminophenoxy)-alpha-substitutedstilbene of claim 2 wherein the aminophenoxy groups are in the paraposition with respect to the X group. 4.4,4'-bis(4-aminophenoxy)-alpha-methylstilbene or4,4'-bis(2-aminophenoxy)-alpha-methylstilbene.